Bridged gallium or indium containing group 4 metal complexes

ABSTRACT

A Group 4 transition metal complex containing a gallium or indium bridging group containing an electron donating group, especially an amido group, linking two groups which may be π-bonding groups or electron donating groups.

CROSS REFERENCE STATEMENT

[0001] This application claims the benefit of U.S. ProvisionalApplication No. 60/172,951, filed Dec. 21, 1999.

BACKGROUND OF THE INVENTION

[0002] This invention relates to certain bridged Group 4 transitionmetal complexes possessing a unique bridging structure and to olefinpolymerization catalysts obtained from such complexes. In one form, thisinvention embodies Group 4 transition metal complexes containing aunique bridged, or divalent ligand structure having two anionic,delocalized π-bonded ligands that are joined by a gallium or indiumcontaining grouping. In a second embodiment the invention relates toGroup 4 transition metal complexes containing a unique bridged ligandcontaining one of the foregoing anionic, delocalized π-bonded moietiesand one anionic amido or phosphido moiety, or a donor electron paircontaining amino or phosphino moiety, which two moieties are similarlyjoined by a gallium or indium containing grouping. In a third embodimentthe invention relates to Group 4 transition metal complexes containing aunique bridged ligand containing two anionic amido and/or phosphidogroups joined by a gallium or indium containing grouping. Catalystcompositions comprising the foregoing metal complexes and their use inaddition polymerizations are also disclosed and claimed.

[0003] In Angew. Chem. Int. Ed. Engl., 36, 21, p2338-2340 (1997) and inPhosphorus, Sulfur, and Silicon, 124 & 125, p561-565 (1997) amidosubstituted boron bridged ferrocenophanes useful for formingpoly(ferrocenes) by a ring opening polymerization were disclosed. Thesynthesis and characterization of Group 1 and 2 metal and tin complexesof 1,2-bis(dimethylamino)-1,2-di-9-fluorenyldiboranes were disclosed inChem. Ber., 127, p1901-1908, (1994). Diboranes having structure similarto those employed in the foregoing study were disclosed by the sameresearchers in Eur. J. Inorg. Chem., p505-509 (1998). Ferrocenophanederivatives of similar bisboranes for further molecular property studieswere disclosed by J. Organomet. Chem., 530 p 117-120 (1997). InOrganometallics, 16, p4546-4550 (1997) boron bridged ansa metallocenecomplexes including dimethylsulfide and phosphine adducts thereof ofpossible use in Ziegler-Natta-type olefin polymerizations weredisclosed.

[0004] In the patent literature, bridged metal complexes for use asolefin polymerization catalyst components, including such complexescontaining one or more boron atoms in the bridge are genericallydisclosed by EP-A-416,815 and WO 98/39369. Generally, gallium or indiumcontaining groups are unknown in metal complexes of the prior art.

SUMMARY OF THE INVENTION

[0005] The present invention relates to certain bridged Group 4transition metal complexes and to olefin polymerization catalystsobtained there from, said complexes corresponding to the followingformula:

[0006] wherein:

[0007] M is titanium, zirconium, or hafnium in the +4,+3, or +2oxidation state;

[0008] Y¹ and Y² are independently an anionic or neutral, cyclic ornon-cyclic, π-bonded group, NR¹, PR¹; NR¹ ₂, PR¹, or (R**)₃—P═N—;

[0009] R** is in one occurrence a covalent bond to Z and in allremaining occurrences a monovalent ligand, illustrated by hydrogen,halogen, or C₁₋₁₀ hydrocarbyl, or two R** groups together form adivalent ligand,

[0010] Z is gallium or indium;

[0011] Q is a neutral, anionic or dianionic ligand group depending onthe oxidation state of M;

[0012] j is 1 or 2 depending on the oxidation state of M and theelectronic nature of Q;

[0013] t is 1 or 2, and when t is 2 there is a direct Z—Z bond;

[0014] T independently each occurrence is: —OR¹, —SR¹, —NR¹ ₂, —PR¹ ₂,—N═CR¹ ₂, —N═PR¹ ₃,

[0015] R¹ is independently each occurrence hydrogen, a hydrocarbylgroup, a tri(hydrocarbyl)silyl group, or atri(hydrocarbyl)silylhydrocarbyl group, said R¹ groups containing up to20 atoms not counting hydrogen;

[0016] R⁵ is R¹ or —N(R¹)₂; and

[0017] two R¹ groups together or one or more R¹ groups together with R⁵may optionally be joined to form a ring structure.

[0018] It is understood that the foregoing metal complexes may exist asdimers and that one or more Lewis bases may optionally be coordinatedwith the complex or the dimer thereof and that when Y¹ or Y² are theneutral ligands, NR¹ ₂ or PR¹ ₂, the bond to M is a coordinate-covalentbond rather than a covalent bond, and j=2. In addition, when T is R¹ ₂N,the bond between T and Z, particularly in the compounds of formula 1,may possess double bond characteristics, that is, the resulting groupmay more accurately depicted by the formula R¹ ₂N═Ga or R¹ ₂N═In.

[0019] Additionally, according to the present invention there areprovided unique ligand structures of the following formula 1A:

[0020] wherein Z, T, t, R¹ and R⁵ are as defined above;

[0021] Y^(1′) and Y^(2′) are anionic, cyclic or non-cyclic, π-bondedgroups, NR¹, or PR¹; and

[0022] R⁴ is hydrogen, a trimethylsilyl group or a trimethyl tin group.

[0023] Such ligand groups of Formula 1A are readily prepared bycontacting sources of the anionic groups (Y^(1′)R⁴)⁻ and (Y^(2′)R⁴)⁻,particularly the Grignard or alkali metal salts thereof, with theneutral compound TZY³ or (TZ)₂Y³ ₂, where Y³ is a leaving group,especially halide, either as neat reagents or in an inert solvent,employing temperatures from −100° C. to 150° C.

[0024] Additionally, according to the present invention there isprovided a process for preparing complexes of formula 1 in high racemicpurity in the +2 formal oxidation state by contacting ligand structuresof formula 1A where R⁴ is trimethylsilyl, or deprotonated dianionicderivatives of ligand structures of formula 1A with a Group 4 precursorof the formula 3:

[0025] wherein M and Y³ are defined as above,

[0026] R⁶ independently each occurrence is hydrogen, a hydrocarbylgroup, a tri(hydrocarbyl)silyl group, or atri(hydrocarbyl)silylhydrocarbyl group, said R⁶ groups containing up to20 atoms not counting hydrogen; and

[0027] LB is a Lewis base, especially an ether, amine, or phosphine ofup to 20 carbons.

[0028] The reaction is desirably conducted in an inert solvent,especially an aliphatic or aromatic hydrocarbon or ether, employingtemperatures from −100° C. to 150° C. This technique is similar to thatdisclosed in U.S. patent application 265,641, filed Mar. 10, 1999,differing in that different starting reagents are employed.

[0029] Further according to the present invention there are providedcatalyst compositions suitable for the polymerization of additionpolymerizable monomers comprising one or more metal complexes of formula1 in combination with one or more activating cocatalysts or activated byuse of an activating technique.

[0030] Finally, according to the present invention there is alsoprovided a polymerization process comprising contacting one or moreaddition polymerizable monomers with a catalyst composition comprisingone or more metal complexes of formula 1 in combination with one or moreactivating cocatalysts or activated by use of an activating technique.The polymerization is preferably performed under solution, slurry,suspension, or high pressure process conditions, and the catalystcomposition or individual components thereof may be used in aheterogeneous state, that is, supported on an inert support, or in ahomogeneous state as dictated by process conditions. The catalysts ofthe present invention can be used in combination with one or moreadditional catalysts of the same or different nature eithersimultaneously or sequentially in the same or in separate reactors.

[0031] Catalyst compositions according to the present invention possessimproved catalytic efficiencies and improved thermal stability,especially when supported on an inert support, allowing for use underhigher operating temperatures compared to catalysts comprisingconventional metal complexes. They are particularly adapted for useunder stereospecific polymerization conditions to provide highly tactic(isotactic or syndiotactic) polyolefin products.

BRIEF DESCRIPTION OF THE DRAWINGS

[0032]FIG. 1 shows the single crystal structure derived by X-rayanalysis (ORTEP) ofBis(dimethylamido)bis(2,6-diisopropylanilide)-indium-t-butyl-N,N′-diisopropylamidinate-titanium(Example 1).

DETAILED DESCRIPTION

[0033] All references to the Periodic Table of the Elements herein shallrefer to the Periodic Table of the Elements, published and copyrightedby CRC Press, Inc., 1999. Also, any references to a Group or Groupsshall be to the Groups or Groups reflected in this Periodic Table of theElements using the IUPAC system for numbering groups. Where any name ofa chemical supplied herein does not correspond to a formula or structureof such chemical, the formula or structure shall control. For purposesof prosecution in the United States of America, where any reference ismade herein to any publication, patent application or provisional patentapplication, the contents thereof are incorporated herein in theirentirety by reference. By the term “π-bonded” as used herein is meantthat bonding occurs through an interaction involving delocalizedelectrons. As used herein the term “comprising” is not intended toexclude any additional component, additive or step. Finally, by theterm, “leaving group” is meant a ligand that is readily displaced byanother ligand under ligand exchange conditions.

[0034] The present Group 4 transition metal complexes contain a uniquebridging group: (T-Z) or (T-Z)₂, which imparts improved catalyticproperties when used in combination with one or more activatingcocatalysts or activating techniques in the presence of additionpolymerizable monomers. While not desiring to be bound by theory, it isbelieved that the improvement in catalytic properties for such complexesmay be due to the electronic properties of the (TZ)_(t), Y¹ and Y²moieties.

[0035] Suitable Y¹ and Y² groups are π-bonded anionic or neutral ligandgroups, which may be cyclic or non-cyclic delocalized π-bonded anionicligand groups. Exemplary of such π-bonded groups are conjugated ornonconjugated, cyclic or non-cyclic dienyl groups, allyl groups,boratabenzene groups, phosphole, and arene groups. Each atom in thedelocalized π-bonded group may independently be substituted with aradical selected from the group consisting of hydrogen, halogen,hydrocarbyl, halohydrocarbyl, hydrocarbyl-substituted metalloid radicalswherein the metalloid is selected from Group 14 of the Periodic Table ofthe Elements, and such hydrocarbyl- or hydrocarbyl-substituted metalloidradicals further substituted with a Group 15 or 16 hetero atomcontaining moiety. Included within the term “hydrocarbyl” are C₁₋₂₀straight, branched and cyclic alkyl radicals, C₆₋₂₀ aromatic radicals,C₇₋₂₀ alkyl-substituted aromatic radicals, and C₇₋₂₀ aryl-substitutedalkyl radicals. In addition two or more such radicals may together forma fused ring system, including partially or fully hydrogenated fusedring systems, or they may form a metallocycle with the metal. Suitablehydrocarbyl-substituted organometalloid radicals include mono-, di- andtri-substituted organometalloid radicals of Group 14 elements whereineach of the hydrocarbyl groups contains from 1 to 20 carbon atoms.Examples of suitable hydrocarbyl-substituted organometalloid radicalsinclude trimethylsilyl, triethylsilyl, ethyldimethylsilyl,methyldiethyl-silyl, triphenylgermyl, and trimethylgermyl groups.Examples of Group 15 or 16 hetero atom containing moieties includeamine, phosphine, ether or thioether moieties or divalent derivativesthereof, e.g. amide, phosphide, ether or thioether groups bonded to thetransition metal or Lanthanide metal, and bonded to the hydrocarbylgroup or to the hydrocarbyl-substituted metalloid containing group.

[0036] Examples of suitable anionic, delocalized π-bonded groups includecyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl,tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl,dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl groups,phosphole, and boratabenzene groups, as well as hydrocarbyl-silyl-(including mono-, di-, or tri(hydrocarbyl)silyl) substituted derivativesthereof. Preferred anionic, delocalized π-bonded groups arecyclopentadienyl, pentamethylcyclopentadienyl,tetramethylcyclopentadienyl,tetramethyl(trimethylsilyl)cyclopentadienyl, inden-1-yl,2,3-dimethylinden-1-yl, fluorenyl, 2-methylinden-1-yl,2-methyl-4-phenylinden-1-yl, 3-(1-pyrrolidinyl)inden-1-yl,tetrahydrofluorenyl, octahydrofluorenyl, and tetrahydroindenyl.

[0037] Boratabenzene groups are anionic ligands that are charged boroncontaining analogues to benzene. They are previously known in the arthaving been described by G. Herberich, et al., in Organometallics, 14,1,471-480 (1995). Preferred boratabenzene ligands correspond to theformula:

[0038] wherein R″ is selected from the group consisting of hydrocarbyl,silyl, N,N-dihydrocarbylamino, or germyl, said R″ having up to 20non-hydrogen atoms. In complexes involving divalent derivatives of suchdelocalized π-bonded groups one atom thereof is bonded by means of acovalent bond or a covalently bonded divalent group to another atom ofthe complex thereby forming a bridged system.

[0039] Phospholes are anionic ligands that are phosphorus containinganalogues to a cyclopentadienyl group. They are previously known in theart having been described by WO 98/50392, and elsewhere. Preferredphosphole ligands correspond to the formula:

[0040] wherein R″ is selected from the group consisting of hydrocarbyl,silyl, N,N-dihydrocarbylamino, or germyl, said R″ having up to 20non-hydrogen atoms, and optionally one or more R″ groups may be bondedtogether forming a multicyclic fused ring system, or form a bridginggroup connected to the metal. In complexes involving divalentderivatives of such delocalized π-bonded groups one atom thereof isbonded by means of a covalent bond or a covalently bonded divalent groupto another atom of the complex thereby forming a bridged system.

[0041] Phosphinimine containing complexes (i.e., wherein Y¹ or Y² is(R**)₃—P═N—) are known in the art, having been previously disclosed inEP-A-890581.

[0042] Preferred Group 4 transition metal complexes of the presentinvention which correspond to formula 1 are represented in formulas 4,5, 6, and 7:

[0043] wherein M, Z, T, Q, t and j are as defined above with respect toformula 1;

[0044] R² is hydrogen, or a hydrocarbyl, halohydrocarbyl,dihydrocarbylamino-hydrocarbyl, tri(hydrocarbylsilyl)hydrocarbyl,Si(R³)₃, N(R³)₂, or OR³ group of up to 20 carbon or silicon atoms, andoptionally two adjacent R² groups can be joined together, therebyforming a fused ring structure, especially an indenyl ligand or asubstituted indenyl ligand;

[0045] R³ is independently hydrogen, a hydrocarbyl group, atrihydrocarbylsilyl group or a trihydrocarbylsilylhydrocarbyl group,said R³ having up to 20 atoms not counting hydrogen; and

[0046] Y is nitrogen or phosphorous.

[0047] When M is in the +4 oxidation state, in formula 4, j=2 and Qindependently each occurrence is halide, hydride, hydrocarbyl,trihydrocarbylsilylhydrocarbyl, hydrocarbyloxide, dihydrocarbylamide,said Q having up to 20 atoms not counting hydrogen. Alternatively, two Qgroups may be joined together to form an alkanediyl- orsilylenebisalkylene-group or a conjugated C₄₋₄₀ diene ligand which iscoordinated to M in a metallocyclopentene fashion.

[0048] When M is in the +3 oxidation state, in formula 5, j=1 and Q iseither 1) a monovalent anionic stabilizing ligand selected from thegroup consisting of alkyl, cycloalkyl, aryl, silyl, amido, phosphido,alkoxy, aryloxy, sulfido groups, and mixtures thereof, and being furthersubstituted with an amine, phosphine, ether, or thioether containingsubstituent able to form a coordinate-covalent bond or chelating bondwith M said ligand having up to 50 atoms not counting hydrogen; or 2) aC₃₋₁₀ hydrocarbyl group comprising an ethylenic unsaturation able toform an η³ bond with M.

[0049] Also, when M is in the +3 oxidation state, in formula 6, j=2, Qindependently each occurrence is halide, hydride, hydrocarbyl,silylhydrocarbyl, hydrocarbyloxide, dihydrocarbylamide, said Q having upto 20 atoms not counting hydrogen. Alternatively, two Q groups may bejoined together to form an alkanediyl group or a conjugated C₄₋₄₀ dieneligand which is coordinated to M in a metallocyclopentene fashion.

[0050] When M is in the +2 oxidation state, in formula 4, j=1 and Q is aneutral conjugated diene, optionally substituted with one or moretri(hydrocarbyl)silyl or tri(hydrocarbylsilyl)hydrocarbyl groups, said Qhaving up to 40 carbon atoms and forming a π-complex with M.

[0051] Specific examples of the above metal complexes wherein M is inthe +4 oxidation state are shown below in formulas 4a, 5a and 7a,wherein the definitions of M, T, t, Z, Y, R¹, R², and R³ are as definedabove with respect to formulas 4-7:

[0052] and wherein j is 2, and Q, independently each occurrence is ahalide, hydrocarbyl, hydrocarbyloxy, or dihydrocarbylamide group of upto 10 atoms not counting hydrogen, or two Q groups together form a C₄₋₂₀diene ligand coordinated to M in a metallocyclopentene fashion. Mosthighly preferably Q independently each occurrence is chloride,trimethylsilylmethyl, or a C₁₋₆ hydrocarbyl group, especially methyl orbenzyl, or two Q groups together form a 2-methyl-1,3-butadienyl or2,3-dimethyl-1,3-butadienyl group.

[0053] Specific examples of the above metal complexes wherein M is inthe +3 oxidation state are shown below in formulas 4b, 4b, 6b and 7b,wherein the definitions of M, Z, T, t, Y, R¹, R², and R³ are as definedabove with respect to formulas 4-7:

[0054] and wherein, for formulas 4b, 5b, and 7b, j is 1, and for formula6b, j is 2; and

[0055] wherein for formulas 4b, 6b and 7b, Q is as defined above, andfor formula 5b, Q is a monovalent anionic stabilizing ligand selectedfrom the group consisting of alkyl, cycloalkyl, aryl, and silyl groupswhich are further substituted with one or more amine, phosphine, orether substituents able to form a coordinate-covalent bond or chelatingbond with M, said Q having up to 30 non-hydrogen atoms; or Q is a C₃₋₁₀hydrocarbyl group comprising an ethylenic unsaturation able to form anbond with M. Most highly preferred examples of such Q ligands are2-N,N-dimethylaminobenzyl, allyl, and 1-methylallyl.

[0056] Specific examples of the above metal complexes wherein M is inthe +2 oxidation state are shown below in formulas 4c, 5c and 7c,wherein the definitions of M, Z, T, t, Y, R¹, R², and R³ are as definedabove with respect to formulas 4-7:

[0057] and wherein j is 1, and Q, each occurrence is a neutralconjugated diene, optionally substituted with one or moretri(hydrocarbyl)silyl groups or tri(hydrocarbyl)silylhydrocarbyl groups,said Q having up to 30 atoms not counting hydrogen and forming aπ-complex with M. Most highly preferred Q groups are1,4-diphenyl-1,3-butadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene,2,4-hexadiene, 1-phenyl-1,3-pentadiene, 1,4-dibenzyl-1,3-butadiene,1,4-ditolyl-1,3-butadiene, 1,4-bis(trimethylsilyl)-1,3-butadiene, and1,4-dinaphthyl-1,3-butadiene.

[0058] Preferably in the foregoing formulas 4, 5, 6, 7, 4a, 4b, 4c, 5a,5b, 5c, 6b, 7a, 7b, and 7c, R¹ independently each occurrence is C₁₋₄alkyl, or phenyl more preferably methyl or isopropyl, most preferablymethyl, Y¹ and Y² are both inden-1-yl,2-(C₁₋₄)alkyl-4-(C₆₋₁₀)arylinden-1-yl, 3-(C₁₋₄)alkylinden-1-yl, or3-(1-pyrrolidinyl)-inden-1-yl), or Y¹ is cyclopentadienyl or(C₁₋₄)alkyl-substituted cyclopentadienyl and Y² is fluorenyl; Z isindium and Q is halide, (C₁₋₄)alkyl, benzyl, or1,4-diphenyl-1,3-butadiene.

[0059] Even more preferably in formulas 4 and 4a-c, M is zirconium orhafnium, Z is indium and R¹ is methyl or isopropyl, most preferablymethyl. During synthesis of these complexes, the use of methyl R¹ groupsgives elevated, often quantitive, yields of the rac isomer. Even morepreferably, in formulas 5, 6, 5a-c, and 6b, M is titanium, Z is indium,Y is nitrogen and R¹ is C₁₋₄ alkyl or phenyl, most preferably methyl orisopropyl.

[0060] Most highly preferred metal complexes are those of formulas 4a,4b, or 4c wherein Y¹ and Y² are both inden-1-yl,2-methyl-4-phenylinden-1-yl, or 2-methyl-4-naphthylinden-1-yl groups,especially compositions comprising greater than 90 percent rac isomer.

[0061] Specific, but not limiting, metal complexes included with theinvention described in the foregoing formulas are:

[0062] dimethylamidogallium-bis-(cyclopentadienyl) zirconium dichloride;

[0063] dimethylamidogallium-bis-(cyclopentadienyl) zirconium dimethyl;

[0064] dimethylamidogallium-bis-(cyclopentadienyl) zirconium2-(N,N-dimethylamino)benzyl;

[0065] dimethylamidogallium-bis-(cyclopentadienyl) zirconium1,4-diphenyl-1,3-butadiene;

[0066] dimethylamidogallium-bis-(n-butylcyclopentadienyl) zirconiumdichloride;

[0067] dimethylamidogallium-bis-(n-butylcyclopentadienyl) zirconiumdimethyl;

[0068] dimethylamidogallium-bis-(n-butylcyclopentadienyl) zirconium2-(N,N-dimethylamino)benzyl;

[0069] dimethylamidogallium-bis-(n-butylcyclopentadienyl) zirconium1,4-diphenyl-1,3-butadiene;

[0070] dimethylamidogallium-bis-(inden-1-yl)zirconium dichloride;

[0071] dimethylamidogallium-bis-(inden-1-yl)zirconium dimethyl;

[0072] dimethylamidogallium-bis-(inden-1-yl)zirconium2-(N,N-dimethylamino)benzyl;

[0073] dimethylamidogallium-bis-(inden-1-yl)zirconium 1,4-diphenyl1,3-butadiene;

[0074] dimethylamidogallium-bis-(2-methyl-4-phenylinden-1-yl)zirconiumdichloride;

[0075] dimethylamidogallium-bis-(2-methyl-4-phenylinden-1-yl)zirconiumdimethyl;

[0076] dimethylamidogallium-bis-(2-methyl-4-phenylinden-1-yl)zirconium2-(N,N-dimethylamino)benzyl;

[0077] dimethylamidogallium-bis-(2-methyl-4-phenylinden-1-yl)zirconium1,4-diphenyl 1,3-butadiene;

[0078] dimethylamidogallium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconiumdichloride;

[0079] dimethylamidogallium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconiumdimethyl;

[0080] dimethylamidogallium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconium2-(N,N-dimethylamino)benzyl;

[0081] dimethylamidogallium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconium1,4-diphenyl-1,3-butadiene;

[0082] diisopropylamidogallium-bis-(cyclopentadienyl) zirconiumdichloride;

[0083] diisopropylamidogallium-bis-(cyclopentadienyl) zirconiumdimethyl;

[0084] diisopropylamidogallium-bis-(cyclopentadienyl) zirconium2-(N,N-dimethylamino)benzyl;

[0085] diisopropylamidogallium-bis-(cyclopentadienyl) zirconium1,4-diphenyl-1,3-butadiene;

[0086] diisopropylamidogallium-bis-(n-butylcyclopentadienyl) zirconiumdichloride;

[0087] diisopropylamidogallium-bis-(n-butylcyclopentadienyl) zirconiumdimethyl;

[0088] diisopropylamidogallium-bis-(n-butylcyclopentadienyl) zirconium2-(N,N-dimethylamino)benzyl;

[0089] diisopropylamidogallium-bis-(n-butylcyclopentadienyl) zirconium1,4-diphenyl-1,3-butadiene;

[0090] diisopropylamidogallium-bis-(inden-1-yl)zirconium dichloride;

[0091] diisopropylamidogallium-bis-(inden-1-yl)zirconium dimethyl;

[0092] diisopropylamidogallium-bis-(inden-1-yl)zirconium2-(N,N-dimethylamino)benzyl;

[0093] diisopropylamidogallium-bis-(inden-1-yl)zirconium1,4-diphenyl1,3-butadiene;

[0094]diisopropylamidogallium-bis-(2-methyl-4-phenylinden-1-yl)zirconiumdichloride;

[0095]diisopropylamidogallium-bis-(2-methyl-4-phenylinden-1-yl)zirconiumdimethyl;

[0096]diisopropylamidogallium-bis-(2-methyl-4-phenylinden-1-yl)zirconium2-(N,N-dimethylamino)benzyl;

[0097]diisopropylamidogallium-bis-(2-methyl-4-phenylinden-1-yl)zirconium1,4-diphenyl 1,3-butadiene;

[0098]diisopropylamidogallium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconiumdichloride;

[0099]diisopropylamidogallium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconiumdimethyl;

[0100]diisopropylamidogallium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconium2-(N,N-dimethylamino)benzyl;

[0101]diisopropylamidogallium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconium1,4-diphenyl-1,3-butadiene;

[0102] bis(trimethylsilylmethyl)amidogallium-bis-(cyclopentadienyl)zirconium dichloride;

[0103] bis(trimethylsilylmethyl)amidogallium-bis-(cyclopentadienyl)zirconium dimethyl;

[0104] bis(trimethylsilylmethyl)amidogallium-bis-(cyclopentadienyl)zirconium 2-(N,N-dimethylamino)benzyl;

[0105] bis(trimethylsilylmethyl)amidogallium-bis-(cyclopentadienyl)zirconium η⁴-1,4-diphenyl-1,3-butadiene;

[0106]bis(trimethylsilylmethyl)amidogallium-bis-(n-butylcyclopentadienyl)zirconium dichloride;

[0107]bis(trimethylsilylmethyl)amidogallium-bis-(n-butylcyclopentadienyl)zirconium dimethyl;

[0108]bis(trimethylsilylmethyl)amidogallium-bis-(n-butylcyclopentadienyl)zirconium 2-(N,N-dimethylamino)benzyl;

[0109]bis(trimethylsilylmethyl)amidogallium-bis-(n-butylcyclopentadienyl)zirconium η⁴-1,4-diphenyl-1,3-butadiene;

[0110] bis(trimethylsilylmethyl)amidogallium-bis-(inden-1-yl) zirconiumdichloride;

[0111] bis(trimethylsilylmethyl)amidogallium-bis-(inden-1-yl)zirconiumdimethyl;

[0112] bis(trimethylsilylmethyl)amidogallium-bis-(inden-1-yl) zirconium2-(N,N-dimethylamino)benzyl;

[0113] bis(trimethylsilylmethyl)amidogallium-bis-(inden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0114]bis(trimethylsilylmethyl)amidogallium-bis-(2-methyl-4-phenylinden-1-yl)zirconiumdichloride;

[0115]bis(trimethylsilylmethyl)amidogallium-bis-(2-methyl-4-phenylinden-1-yl)zirconiumdimethyl;

[0116]bis(trimethylsilylmethyl)amidogallium-bis-(2-methyl-4-phenylinden-1-yl)zirconium2-(N,N-dimethylamino)benzyl;

[0117]bis(trimethylsilylmethyl)amidogallium-bis-(2-methyl-4-phenylinden-1-yl)zirconiumη⁴-1,4-diphenyl-1,3-butadiene;

[0118]bis(trimethylsilylmethyl)amidogallium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconiumdichloride;

[0119]bis(trimethylsilylmethyl)amidogallium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconiumdimethyl;

[0120]bis(trimethylsilylmethyl)amidogallium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconium2-(N,N-dimethylamino)benzyl;

[0121]bis(trimethylsilylmethyl)amidogallium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconium1,4-diphenyl-1,3-butadiene;

[0122] dimethylamidoindium-bis-(cyclopentadienyl) zirconium dichloride;

[0123] dimethylamidoindium-bis-(cyclopentadienyl) zirconium dimethyl;

[0124] dimethylamidoindium-bis-(cyclopentadienyl) zirconium2-(N,N-dimethylamino)benzyl;

[0125] dimethylamidoindium-bis-(cyclopentadienyl) zirconium1,4-diphenyl-1,3-butadiene;

[0126] dimethylamidoindium-bis-(n-butylcyclopentadienyl) zirconiumdichloride;

[0127] dimethylamidoindium-bis-(n-butylcyclopentadienyl) zirconiumdimethyl;

[0128] dimethylamidoindium-bis-(n-butylcyclopentadienyl) zirconium2-(N,N-dimethylamino)benzyl;

[0129] dimethylamidoindium-bis-(n-butylcyclopentadienyl) zirconium1,4-diphenyl-1,3-butadiene;

[0130] dimethylamidoindium-bis-(inden-1-yl)zirconium dichloride;

[0131] dimethylamidoindium-bis-(inden-1-yl)zirconium dimethyl;

[0132] dimethylamidoindium-bis-(inden-1-yl)zirconium2-(N,N-dimethylamino)benzyl;

[0133] dimethylamidoindium-bis-(inden-1-yl)zirconium 1,4-diphenyl1,3-butadiene;

[0134] dimethylamidoindium-bis-(2-methyl-4-phenylinden-1-yl)zirconiumdichloride;

[0135] dimethylamidoindium-bis-(2-methyl-4-phenylinden-1-yl)zirconiumdimethyl;

[0136] dimethylamidoindium-bis-(2-methyl-4-phenylinden-1-yl)zirconium2-(N,N-dimethylamino)benzyl;

[0137] dimethylamidoindium-bis-(2-methyl-4-phenylinden-1-yl)zirconium1,4-diphenyl 1,3-butadiene;

[0138] dimethylamidoindium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconiumdichloride;

[0139] dimethylamidoindium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconiumdimethyl;

[0140] dimethylamidoindium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconium2-(N,N-dimethylamino)benzyl;

[0141] dimethylamidoindium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconium1,4-diphenyl-1,3-butadiene;

[0142] diisopropylamidoindium-bis-(cyclopentadienyl) zirconiumdichloride;

[0143] diisopropylamidoindium-bis-(cyclopentadienyl) zirconium dimethyl;

[0144] diisopropylamidoindium-bis-(cyclopentadienyl) zirconium2-N,N-dimethylamino)benzyl;

[0145] diisopropylamidoindium-bis-(cyclopentadienyl) zirconium1,4-diphenyl-1,3-butadiene;

[0146] diisopropylamidoindium-bis-(n-butylcyclopentadienyl) zirconiumdichloride;

[0147] diisopropylamidoindium-bis-(n-butylcyclopentadienyl) zirconiumdimethyl;

[0148] diisopropylamidoindium-bis-(n-butylcyclopentadienyl) zirconium2-(N,N-dimethylamino)benzyl;

[0149] diisopropylamidoindium-bis-(n-butylcyclopentadienyl) zirconium1,4-diphenyl-1,3-butadiene;

[0150] diisopropylamidoindium-bis-(inden-1-yl) zirconium dichloride;

[0151] diisopropylamidoindium-bis-(inden-1-yl) zirconium dimethyl;

[0152] diisopropylamidoindium-bis-(inden-1-yl) zirconium2-(N,N-dimethylamino)benzyl;

[0153] diisopropylamidoindium-bis-(inden-1-yl) zirconium1,4-diphenyl1,3-butadiene;

[0154] diisopropylamidoindium-bis-(2-methyl-4-phenylinden-1-yl)zirconiumdichloride;

[0155] diisopropylamidoindium-bis-(2-methyl-4-phenylinden-1-yl)zirconiumdimethyl;

[0156] diisopropylamidoindium-bis-(2-methyl-4-phenylinden-1-yl)zirconium2-(N,N-dimethylamino)benzyl;

[0157] diisopropylamidoindium-bis-(2-methyl-4-phenylinden-1-yl)zirconium1,4-diphenyl 1,3-butadiene;

[0158]diisopropylamidoindium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconiumdichloride;diisopropylamidoindium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconiumdimethyl;

[0159]diisopropylamidoindium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconium2-(N,N-dimethylamino)benzyl;

[0160]diisopropylamidoindium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconium1,4-diphenyl-1,3-butadiene;

[0161] bis(trimethylsilylmethyl)amidoindium-bis-(cyclopentadienyl)zirconium dichloride;

[0162] bis(trimethylsilylmethyl)amidoindium-bis-(cyclopentadienyl)zirconium dimethyl;

[0163] bis(trimethylsilylmethyl)amidoindium-bis-(cyclopentadienyl)zirconium 2-(N,N-dimethylamino)benzyl;

[0164] bis(trimethylsilylmethyl)amidoindium-bis-(cyclopentadienyl)zirconium 1,4-diphenyl-1,3-butadiene;

[0165]bis(trimethylsilylmethyl)amidoindium-bis-(n-butylcyclopentadienyl)zirconium dichloride;

[0166]bis(trimethylsilylmethyl)amidoindium-bis-(n-butylcyclopentadienyl)zirconium dimethyl;

[0167]bis(trimethylsilylmethyl)amidoindium-bis-(n-butylcyclopentadienyl)zirconium 2-(N,N-dimethylamino)benzyl;

[0168]bis(trimethylsilylmethyl)amidoindium-bis-(n-butylcyclopentadienyl)zirconium 1,4-diphenyl-1,3-butadiene;

[0169] bis(trimethylsilylmethyl)amidoindium-bis-(inden-1-yl)zirconiumdichloride;

[0170] bis(trimethylsilylmethyl)amidoindium-bis-(inden-1-yl) zirconiumdimethyl; bis(trimethylsilylmethyl)amidoindium-bis-(inden-1-yl)zirconium2-(N,N-dimethylamino)benzyl;

[0171] bis(trimethylsilylmethyl)amidoindium-bis-(inden-1-yl)zirconium1,4-diphenyl-1,3-butadiene;

[0172]bis(trimethylsilylmethyl)amidoindium-bis-(2-methyl-4-phenylinden-1-yl)zirconiumdichloride;

[0173]bis(trimethylsilylmethyl)amidoindium-bis-(2-methyl-4-phenylinden-1-yl)zirconiumdimethyl;

[0174]bis(trimethylsilylmethyl)amidoindium-bis-(2-methyl-4-phenylinden-1-yl)zirconium2-(N,N-dimethylamino)benzyl;

[0175]bis(trimethylsilylmethyl)amidoindium-bis-(2-methyl-4-phenylinden-1-yl)zirconium1,4-diphenyl-1,3-butadiene;

[0176]bis(trimethylsilylmethyl)amidoindium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconiumdichloride;

[0177]bis(trimethylsilylmethyl)amidoindium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconiumdimethyl;

[0178]bis(trimethylsilylmethyl)amidoindium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconium2-(N,N-dimethylamino)benzyl; and

[0179]bis(trimethylsilylmethyl)amidoindium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconium1,4-diphenyl-1,3-butadiene.

[0180] A further preferred class of Group 4 transition metal complexesof the present invention are represented in previously defined formulas4-7 wherein T is:

[0181] including such structures where two R¹ groups and R⁵ are linkedsuch as in 1,3,4,6,7,8, hexahydro-pyrimido[1,2-a] pyrimidinate, shownbelow:

[0182] In the foregoing species, it is believed, without wishing to bebound by such belief, that the ligand group, T, is connected to Z viathe heteroatoms thereof.

[0183] Specific, but not limiting, examples of the foregoing metalcomplexes included within the invention are:

[0184]1,3-diisopropyl-2-t-butyl-amidinatogallium-bis-(cyclopentadienyl)zirconiumdichloride;

[0185]1,3-diisopropyl-2-t-butyl-amidinatogallium-bis-(cyclopentadienyl)zirconiumdimethyl;

[0186]1,3-diisopropyl-2-t-butyl-amidinatogallum-bis-(cyclopentadienyl)zirconium2-(N,N-dimethylamino)benzyl;

[0187]1,3-diisopropyl-2-t-butyl-amidinatogallium-bis-(cyclopentadienyl)zirconium1,4-diphenyl-1,3-butadiene;

[0188]1,3-diisopropyl-2-t-butyl-amidinatogallium-bis-(n-butylcyclopentadienyl)zirconium dichloride;

[0189]1,3-diisopropyl-2-t-butyl-amidinatogallium-bis-(n-butylcyclopentadienyl)zirconium dimethyl;

[0190]1,3-diisopropyl-2-t-butyl-amidinatogallium-bis-(n-butylcyclopentadienyl)zirconium 2-(N,N-dimethylamino)benzyl;

[0191]1,3-diisopropyl-2-t-butyl-amidinatogallium-bis-(n-butylcyclopentadienyl)zirconium 1,4-diphenyl-1,3-butadiene;

[0192] 1,3-diisopropyl-2-t-butyl-amidinatogallium-bis-(inden-1-yl)zirconium dichloride;

[0193] 1,3-diisopropyl-2-t-butyl-amidinatogallium-bis-(inden-1-yl)zirconium dimethyl;

[0194] 1,3-diisopropyl-2-t-butyl-amidinatogallum-bis-(inden-1-yl)zirconium 2-(N,N-dimethylamino)benzyl;

[0195] 1,3-diisopropyl-2-t-butyl-amidinatogallium-bis-(inden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene;

[0196]1,3-diisopropyl-2-t-butyl-amidinatogallium-bis-(2-methyl-4-phenylinden-1-yl)zirconium dichloride;

[0197]1,3-diisopropyl-2-t-butyl-amidinatogallium-bis-(2-methyl-4-phenylinden-1-yl)zirconium dimethyl;

[0198]1,3-diisopropyl-2-t-butyl-amidinatogallum-bis-(2-methyl-4-phenylinden-1-yl)zirconium 2-(N,N-dimethylamino)benzyl;

[0199]1,3-diisopropyl-2-t-butyl-amidinatogallium-bis-(2-methyl-4-phenylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene;

[0200]1,3-diisopropyl-2-t-butyl-amidinatogallium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconiumdichloride;

[0201]1,3-diisopropyl-2-t-butyl-amidinatogallium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconiumdimethyl;

[0202]1,3-diisopropyl-2-t-butyl-amidinatogallium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconium2-(N,N-dimethylamino)benzyl;

[0203]1,3-diisopropyl-2-t-butyl-amidinatogallium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconium1,4-diphenyl-1,3-butadiene;

[0204]1,3-diisopropyl-2-phenyl-amidinatogallium-bis-(cyclopentadienyl)zirconiumdichloride;

[0205]1,3-diisopropyl-2-phenyl-amidinatogallium-bis-(cyclopentadienyl)zirconiumdimethyl;

[0206]1,3-diisopropyl-2-phenyl-amidinatogallum-bis-(cyclopentadienyl)zirconium2-(N,N-dimethylamino)benzyl;

[0207]1,3-diisopropyl-2-phenyl-amidinatogallium-bis-(cyclopentadienyl)zirconium1,4-diphenyl-1,3-butadiene;

[0208]1,3-diisopropyl-2-phenyl-amidinatogallium-bis-(n-butylcyclopentadienyl)zirconium dichloride;

[0209]1,3-diisopropyl-2-phenyl-amidinatogallium-bis-(n-butylcyclopentadienyl)zirconium dimethyl;

[0210]1,3-diisopropyl-2-phenyl-amidinatogallium-bis-(n-butylcyclopentadienyl)zirconium 2-(N,N-dimethylamino)benzyl;

[0211]1,3-diisopropyl-2-phenyl-amidinatogallium-bis-(n-butylcyclopentadienyl)zirconium 1,4-diphenyl-1,3-butadiene;

[0212] 1,3-diisopropyl-2-phenyl-amidinatogallium-bis-(inden-1-yl)zirconium dichloride;

[0213] 1,3-diisopropyl-2-phenyl-amidinatogallium-bis-(inden-1-yl)zirconium dimethyl;

[0214] 1,3-diisopropyl-2-phenyl-amidinatogallum-bis-(inden-1-yl)zirconium 2-(N,N-dimethylamino)benzyl;

[0215] 1,3-diisopropyl-2-phenyl-amidinatogallium-bis-(inden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene;

[0216]1,3-diisopropyl-2-phenyl-amidinatogallium-bis-(2-methyl-4-phenylinden-1-yl)zirconium dichloride;

[0217]1,3-diisopropyl-2-phenyl-amidinatogallium-bis-(2-methyl-4-phenylinden-1-yl)zirconium dimethyl;

[0218]1,3-diisopropyl-2-phenyl-amidinatogallum-bis-(2-methyl-4-phenylinden-1-yl)zirconium 2-(N,N-dimethylamino)benzyl;

[0219]1,3-diisopropyl-2-phenyl-amidinatogallium-bis-(2-methyl-4-phenylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene;

[0220]1,3-diisopropyl-2-phenyl-amidinatogallium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconiumdichloride;

[0221]1,3-diisopropyl-2-phenyl-amidinatogallium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconiumdimethyl;

[0222]1,3-diisopropyl-2-phenyl-amidinatogallium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconium2-(N,N-dimethylamino)benzyl;

[0223]1,3-diisopropyl-2-phenyl-amidinatogallium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconium1,4-diphenyl-1,3-butadiene;

[0224] N,N′-diisopropyl-3-t-butyl-1,3-diketiminegallium-bis-(cyclopentadienyl)zirconium dichloride;

[0225] N,N′-diisopropyl-3-t-butyl-1,3-diketiminegallium-bis-(cyclopentadienyl)zirconium dimethyl;

[0226] N,N′-diisopropyl-3-t-butyl-1,3-diketiminegallium-bis-(cyclopentadienyl)zirconium 2-(N,N-dimethylamino)benzyl;

[0227] N,N′-diisopropyl-3-t-butyl-1,3-diketiminegallium-bis-(cyclopentadienyl)zirconium 1,diphenyl-1,3-butadiene;

[0228] N,N′-diisopropyl-3-t-butyl-1,3-diketiminegallium-bis-(n-butylcyclopentadienyl) zirconium dichloride;

[0229] N,N′-diisopropyl-3-t-butyl-1,3-diketiminegallium-bis-(n-butylcyclopentadienyl) zirconium dimethyl;

[0230] N,N′-diisopropyl-3-t-butyl-1,3-diketiminegallium-bis-(n-butylcyclopentadienyl) zirconium2-(N,N-dimethylamino)benzyl;

[0231] N,N′-diisopropyl-3-t-butyl-1,3-diketiminegallium-bis-(n-butylcyclopentadienyl) zirconium1,diphenyl-1,3-butadiene;

[0232] N,N ′-diisopropyl-3-t-butyl-1,3-diketiminegallium-bis-(inden-1-yl)zirconium dichloride;

[0233] N,N′-diisopropyl-3-t-butyl-1,3-diketiminegallium-bis-(inden-1-yl)zirconium dimethyl;

[0234] N,N′-diisopropyl-3-t-butyl-1,3-diketiminegallium-bis-(inden-1-yl)zirconium 2-(N,N-dimethylamino)benzyl;

[0235] N,N ′-diisopropyl-3-t-butyl-1,3-diketiminegallium-bis-(inden-1-yl)zirconium 1,diphenyl-1,3-butadiene;

[0236] N,N′-diisopropyl-3-t-butyl-1,3-diketiminegallium-bis-(2-methyl-4-phenylinden-1-yl)zirconium dichloride;

[0237] N,N′-diisopropyl-3-t-butyl-1,3-diketiminegallium-bis-(2-methyl-4-phenylinden-1-yl)zirconium dimethyl;

[0238] N,N ′-diisopropyl-3-t-butyl-1,3-diketiminegallium-bis-(2-methyl-4-phenylinden-1-yl)zirconium2-(N,N-dimethylamino)benzyl;

[0239] N,N′-diisopropyl-3-t-butyl-1,3-diketiminegallium-bis-(2-methyl-4-phenylinden-1-yl)zirconium1,diphenyl-1,3-butadiene;

[0240] N,N′-diisopropyl-3-t-butyl-1,3-diketiminegallium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconium dichloride;

[0241] N,N′-diisopropyl-3-t-butyl-1,3-diketiminegallium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconium dimethyl;

[0242] N,N′-diisopropyl-3-t-butyl-1,3-diketiminegallium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconium2-(N,N-dimethylamino)benzyl;

[0243] N,N′-diisopropyl-3-t-butyl-1,3-diketiminegallium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconium1,diphenyl-1,3-butadiene;

[0244] N,N′-diisopropyl-3-phenyl-1,3-diketiminegallium-bis-(cyclopentadienyl) zirconium dichloride;

[0245] N,N′-diisopropyl-3-phenyl-1,3-diketiminegallium-bis-(cyclopentadienyl) zirconium dimethyl;

[0246] N,N′-diisopropyl-3-phenyl-1,3-diketiminegallium-bis-(cyclopentadienyl) zirconium 2-(N,N-dimethylamino)benzyl;

[0247] N,N′-diisopropyl-3-phenyl-1,3-diketiminegallium-bis-(cyclopentadienyl) zirconium 1,diphenyl-1,3-butadiene;

[0248] N,N′-diisopropyl-3-phenyl-1,3-diketiminegallium-bis-(n-butylcyclopentadienyl) zirconium dichloride;

[0249] N,N′-diisopropyl-3-phenyl-1,3-diketiminegallium-bis-(n-butylcyclopentadienyl) zirconium dimethyl;

[0250] N,N′-diisopropyl-3-phenyl-1,3-diketiminegallium-bis-(n-butylcyclopentadienyl) zirconium2-(N,N-dimethylamino)benzyl;

[0251] N,N′-diisopropyl-3-phenyl-1,3-diketiminegallium-bis-(n-butylcyclopentadienyl) zirconium1,diphenyl-1,3-butadiene;

[0252] N,N′-diisopropyl-3-phenyl-1,3-diketimine gallium-bis-(inden-1-yl)zirconium dichloride;

[0253] N,N′-diisopropyl-3-phenyl-1,3-diketimine gallium-bis-(inden-1-yl)zirconium dimethyl;

[0254] N,N′-diisopropyl-3-phenyl-1,3-diketimine gallium-bis-(inden-1-yl)zirconium 2-(N,N-dimethylamino)benzyl;

[0255] N,N′-diisopropyl-3-phenyl-1,3-diketimine gallium-bis-(inden-1-yl)zirconium 1,diphenyl-1,3-butadiene;

[0256] N,N′-diisopropyl-3-phenyl-1,3-diketiminegallium-bis-(2-methyl-4-phenylinden-1-yl) zirconium dichloride;

[0257] N,N′-diisopropyl-3-phenyl-1,3-diketiminegallium-bis-(2-methyl-4-phenylinden-1-yl) zirconium dimethyl;

[0258] N,N′-diisopropyl-3-phenyl-1,3-diketiminegallium-bis-(2-methyl-4-phenylinden-1-yl) zirconium2-(N,N-dimethylamino)benzyl;

[0259] N,N′-diisopropyl-3-phenyl-1,3-diketiminegallium-bis-(2-methyl-4-phenylinden-1-yl) zirconium1,diphenyl-1,3-butadiene;

[0260] N,N′-diisopropyl-3-phenyl-1,3-diketiminegallium-bis-(3-(1-pyrrolidinyl)inden-1-yl) zirconium dichloride;

[0261] N,N′-diisopropyl-3-phenyl-1,3-diketiminegallium-bis-(3-(1-pyrrolidinyl)inden-1-yl) zirconium dimethyl;

[0262] N,N′-diisopropyl-3-phenyl-1,3-diketiminegallium-bis-(3-(1-pyrrolidinyl)inden-1-yl) zirconium2-(N,N-dimethylamino)benzyl;

[0263] N,N′-diisopropyl-3-phenyl-1,3-diketiminegallium-bis-(3-(1-pyrrolidinyl)inden-1-yl) zirconium1,diphenyl-1,3-butadiene;

[0264] N,N′-diisopropyl-dimethylguanidinategallium-bis-(cyclopentadienyl) zirconium dichloride;

[0265] N,N′-diisopropyl-dimethylguanidinategallium-bis-(cyclopentadienyl) zirconium dimethyl;

[0266] N,N′-diisopropyl-dimethylguanidinategallium-bis-(cyclopentadienyl) zirconium 2-(N,N-dimethylamino)benzyl;

[0267] N,N′-diisopropyl-dimethylguanidinategallium-bis-(cyclopentadienyl) zirconium 1,diphenyl-1,3-butadiene;

[0268] N,N′-diisopropyl-dimethylguanidinategallium-bis-(n-butylcyclopentadienyl) zirconium dichloride;

[0269] N,N′-diisopropyl-dimethylguanidinategallium-bis-(n-butylcyclopentadienyl) zirconium dimethyl;

[0270] N,N′-diisopropyl-dimethylguanidinategallium-bis-(n-butylcyclopentadienyl) zirconium2-(N,N-dimethylamino)benzyl;

[0271] N,N′-diisopropyl-dimethylguanidinategallium-bis-(n-butylcyclopentadienyl) zirconium1,diphenyl-1,3-butadiene;

[0272] N,N′-diisopropyl-dimethylguanidinate gallium-bis-(inden-1-yl)zirconium dichloride;

[0273] N,N′-diisopropyl-dimethylguanidinate gallium-bis-(inden-1-yl)zirconium dimethyl;

[0274] N,N′-diisopropyl-dimethylguanidinate gallium-bis-(inden-1-yl)zirconium 2-(N,N-dimethylamino)benzyl;

[0275] N,N′-diisopropyl-dimethylguanidinate gallium-bis-(inden-1-yl)zirconium 1,diphenyl-1,3-butadiene;

[0276] N,N′-diisopropyl-dimethylguanidinategallium-bis-(2-methyl-4-phenylinden-1-yl) zirconium dichloride;

[0277] N,N′-diisopropyl-dimethylguanidinategallium-bis-(2-methyl-4-phenylinden-1-yl) zirconium dimethyl;

[0278] N,N′-diisopropyl-dimethylguanidinategallium-bis-(2-methyl-4-phenylinden-1-yl) zirconium2-(N,N-dimethylamino)benzyl;

[0279] N,N′-diisopropyl-dimethylguanidinategallium-bis-(2-methyl-4-phenylinden-1-yl) zirconium1,diphenyl-1,3-butadiene;

[0280] N,N′-diisopropyl-dimethylguanidinategallium-bis-(3-(1-pyrrolidinyl)inden-1-yl) zirconium dichloride;

[0281] N,N′-diisopropyl-dimethylguanidinategallium-bis-(3-(1-pyrrolidinyl)inden-1-yl) zirconium dimethyl;

[0282] N,N′-diisopropyl-dimethylguanidinategallium-bis-(3-(1-pyrrolidinyl)inden-1-yl) zirconium2-(N,N-dimethylamino)benzyl;

[0283] N,N′-diisopropyl-dimethylguanidinategallium-bis-(3-(1-pyrrolidinyl)inden-1-yl) zirconium1,diphenyl-1,3-butadiene;

[0284] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinategallium-bis-(cyclopentadienyl)zirconium dichloride;

[0285] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinategallium-bis-(cyclopentadienyl)zirconium dimethyl;

[0286] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinategallium-bis-(cyclopentadienyl)zirconium 2-(N,N-dimethylamino)benzyl;

[0287] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinategallium-bis-(cyclopentadienyl)zirconium 1,diphenyl-1,3-butadiene;

[0288] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinategallium-bis-(n-butylcyclopentadienyl) zirconium dichloride;

[0289] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinategallium-bis-(n-butylcyclopentadienyl) zirconium dimethyl;

[0290] 1,3,4,6,7,8-hexahydro-pyrimido [1,2-a] pyrimidinategallium-bis-(n-butylcyclopentadienyl) zirconium2-(N,N-dimethylamino)benzyl;

[0291] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinategallium-bis-(n-butylcyclopentadienyl) zirconium1,diphenyl-1,3-butadiene;

[0292] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinategallium-bis-(inden-1-yl) zirconium dichloride;

[0293] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinategallium-bis-(inden-1-yl) zirconium dimethyl;

[0294] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinategallium-bis-(inden-1-yl) zirconium 2-(N,N-dimethylamino)benzyl;

[0295] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinategallium-bis-(inden-1-yl) zirconium 1,diphenyl-1,3-butadiene;

[0296] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinategallium-bis-(2-methyl-4-phenylinden-1-yl) zirconium dichloride;

[0297] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinategallium-bis-(2-methyl-4-phenylinden-1-yl) zirconium dimethyl;

[0298] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinategallium-bis-(2-methyl-4-phenylinden-1-yl) zirconium2-(N,N-dimethylamino)benzyl;

[0299] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinategallium-bis-(2-methyl-4-phenylinden-1-yl) zirconium1,diphenyl-1,3-butadiene;

[0300] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinategallium-bis-(3-(1-pyrrolidinyl)inden-1-yl) zirconium dichloride;

[0301] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinategallium-bis-(3-(1-pyrrolidinyl)inden-1-yl) zirconium dimethyl;

[0302] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinategallium-bis-(3-(1-pyrrolidinyl)inden-1-yl) zirconium2-(N,N-dimethylamino)benzyl;

[0303] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinategallium-bis-(3-(1-pyrrolidinyl)inden-1-yl) zirconium1,diphenyl-1,3-butadiene;

[0304]1,3-diisopropyl-2-t-butyl-amidinatoindium-bis-(cyclopentadienyl)zirconiumdichloride;

[0305]1,3-diisopropyl-2-t-butyl-amidinatoindium-bis-(cyclopentadienyl)zirconiumdimethyl;

[0306]1,3-diisopropyl-2-t-butyl-amidinatogallum-bis-(cyclopentadienyl)zirconium2-(N,N-dimethylamino)benzyl;

[0307]1,3-diisopropyl-2-t-butyl-amidinatoindium-bis-(cyclopentadienyl)zirconium1,4-diphenyl-1,3-butadiene;

[0308]1,3-diisopropyl-2-t-butyl-amidinatoindium-bis-(n-butylcyclopentadienyl)zirconium dichloride;

[0309]1,3-diisopropyl-2-t-butyl-amidinatoindium-bis-(n-butylcylopentadienyl)zirconium dimethyl;

[0310]1,3-diisopropyl-2-t-butyl-amidinatoindium-bis-(n-butylcyclopentadienyl)zirconium 2-(N,N-dimethylamino)benzyl;

[0311]1,3-diisopropyl-2-t-butyl-amidinatoindium-bis-(n-butylcyclopentadienyl)zirconium 1,4-diphenyl-1,3-butadiene;

[0312]1,3-diisopropyl-2-t-butyl-amidinatoindium-bis-(inden-1-yl)zirconium dichloride;

[0313] 1,3-diisopropyl-2-t-butyl-amidinatoindium-bis-(inden-1-yl)zirconium dimethyl;

[0314] 1,3-diisopropyl-2-t-butyl-amidinatogallum-bis-(inden-1-yl)zirconium 2-(N,N-dimethylamino)benzyl;

[0315] 1,3-diisopropyl-2-t-butyl-amidinatoindium-bis-(inden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene;

[0316]1,3-diisopropyl-2-t-butyl-amidinatoindium-bis-(2-methyl-4-phenylinden-1-yl)zirconium dichloride;

[0317]1,3-diisopropyl-2-t-butyl-amidinatoindium-bis-(2-methyl-4-phenylinden-1-yl)zirconium dimethyl;

[0318]1,3-diisopropyl-2-t-butyl-amidinatogallum-bis-(2-methyl-4-phenylinden-1-yl)zirconium 2-(N,N-dimethylamino)benzyl;

[0319]1,3-diisopropyl-2-t-butyl-amidinatoindium-bis-(2-methyl-4-phenylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene;

[0320]1,3-diisopropyl-2-t-butyl-amidinatoindium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconiumdichloride;

[0321]1,3-diisopropyl-2-t-butyl-amidinatoindium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconiumdimethyl;

[0322]1,3-diisopropyl-2-t-butyl-amidinatoindium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconium2-(N,N-dimethylamino)benzyl;

[0323]1,3-diisopropyl-2-t-butyl-amidinatoindium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconium1,4-diphenyl-1,3-butadiene;

[0324]1,3-diisopropyl-2-phenyl-amidinatoindium-bis-(cyclopentadienyl)zirconiumdichloride;

[0325]1,3-diisopropyl-2-phenyl-amidinatoindium-bis-(cyclopentadienyl)zirconiumdimethyl;

[0326]1,3-diisopropyl-2-phenyl-amidinatogallum-bis-(cyclopentadienyl)zirconium2-(N,N-dimethylamino)benzyl;

[0327]1,3-diisopropyl-2-phenyl-amidinatoindium-bis-(cyclopentadienyl)zirconium1,4-diphenyl-1,3-butadiene;

[0328]1,3-diisopropyl-2-phenyl-amidinatoindium-bis-(n-butylcyclopentadienyl)zirconium dichloride;

[0329]1,3-diisopropyl-2-phenyl-amidinatoindium-bis-(n-butylcyclopentadienyl)zirconium dimethyl;

[0330]1,3-diisopropyl-2-phenyl-amidinatoindium-bis-(n-butylcyclopentadienyl)zirconium 2-(N,N-dimethylamino)benzyl;

[0331]1,3-diisopropyl-2-phenyl-amidinatoindium-bis-(n-butylcyclopentadienyl)zirconium 1,4-diphenyl-1,3-butadiene;

[0332] 1,3-diisopropyl-2-phenyl-amidinatoindium-bis-(inden-1-yl)zirconium dichloride;

[0333] 1,3-diisopropyl-2-phenyl-amidinatoindium-bis-(inden-1-yl)zirconium dimethyl;

[0334] 1,3-diisopropyl-2-phenyl-amidinatogallum-bis-(inden-1-yl)zirconium 2-(N,N-dimethylamino)benzyl;

[0335] 1,3-diisopropyl-2-phenyl-amidinatoindium-bis-(inden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene;

[0336]1,3-diisopropyl-2-phenyl-amidinatoindium-bis-(2-methyl-4-phenylinden-1-yl)zirconium dichloride;

[0337]1,3-diisopropyl-2-phenyl-amidinatoindium-bis-(2-methyl-4-phenylinden-1-yl)zirconium dimethyl;

[0338]1,3-diisopropyl-2-phenyl-amidinatogallum-bis-(2-methyl-4-phenylinden-1-yl)zirconium 2-(N,N-dimethylamino)benzyl;

[0339]1,3-diisopropyl-2-phenyl-amidinatoindium-bis-(2-methyl-4-phenylinden-1-yl)zirconium 1,4-diphenyl-1,3-butadiene;

[0340]1,3-diisopropyl-2-phenyl-amidinatoindium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconiumdichloride;

[0341]1,3-diisopropyl-2-phenyl-amidinatoindium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconiumdimethyl;

[0342]1,3-diisopropyl-2-phenyl-amidinatoindium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconium2-(N,N-dimethylamino)benzyl;

[0343]1,3-diisopropyl-2-phenyl-amidinatoindium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconium1,4-diphenyl-1,3-butadiene;

[0344] N,N′-diisopropyl-3-t-butyl-1,3-diketimineindium-bis-(cyclopentadienyl) zirconium dichloride;

[0345] N,N′-diisopropyl-3-t-butyl-1,3-diketimineindium-bis-(cyclopentadienyl) zirconium dimethyl;

[0346] N,N′-diisopropyl-3-t-butyl-1,3-diketimineindium-bis-(cyclopentadienyl) zirconium 2-(N,N-dimethylamino)benzyl;

[0347] N,N′-diisopropyl-3-t-butyl-1,3-diketimineindium-bis-(cyclopentadienyl) zirconium 1,diphenyl-1,3-butadiene;

[0348] N,N′-diisopropyl-3-t-butyl-1,3-diketimineindium-bis-(n-butylcyclopentadienyl)zirconium dichloride;

[0349] N,N′-diisopropyl-3-t-butyl-1,3-diketimineindium-bis-(n-butylcyclopentadienyl)zirconium dimethyl;

[0350] N,N′-diisopropyl-3-t-butyl-1,3-diketimineindium-bis-(n-butylcyclopentadienyl)zirconium2-(N,N-dimethylamino)benzyl;

[0351] N,N′-diisopropyl-3-t-butyl-1,3-diketimineindium-bis-(n-butylcyclopentadienyl)zirconium 1,diphenyl-1,3-butadiene;

[0352] N,N′-diisopropyl-3-t-butyl-1,3-diketimineindium-bis-(inden-1-yl)zirconium dichloride;

[0353] N,N′-diisopropyl-3-t-butyl-1,3-diketimineindium-bis-(inden-1-yl)zirconium dimethyl;

[0354] N,N′-diisopropyl-3-t-butyl-1,3-diketimineindium-bis-(inden-1-yl)zirconium 2-(N,N-dimethylamino)benzyl;

[0355] N,N′-diisopropyl-3-t-butyl-1,3-diketimineindium-bis-(inden-1-yl)zirconium 1,diphenyl-1,3-butadiene;

[0356] N,N′-diisopropyl-3-t-butyl-1,3-diketimineindium-bis-(2-methyl-4-phenylinden-1-yl)zirconium dichloride;

[0357] N,N′-diisopropyl-3-t-butyl-1,3-diketimineindium-bis-(2-methyl-4-phenylinden-1-yl)zirconium dimethyl;

[0358] N,N′-diisopropyl-3-t-butyl-1,3-diketimineindium-bis-(2-methyl-4-phenylinden-1-yl)zirconium2-(N,N-dimethylamino)benzyl;

[0359] N,N′-diisopropyl-3-t-butyl-1,3-diketimineindium-bis-(2-methyl-4-phenylinden 1-yl)zirconium1,diphenyl-1,3-butadiene;

[0360] N,N′-diisopropyl-3-t-butyl-1,3-diketimineindium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconium dichloride;

[0361] N,N′-diisopropyl-3-t-butyl-1,3-diketimineindium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconium dimethyl;

[0362] N,N′-diisopropyl-3-t-butyl-1,3-diketimineindium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconium2-(N,N-dimethylamino)benzyl;

[0363] N,N′-diisopropyl-3-t-butyl-1,3-diketimineindium-bis-(3-(1-pyrrolidinyl)inden-1-yl)zirconium1,diphenyl-1,3-butadiene;

[0364] N,N′-diisopropyl-3-phenyl-1,3-diketimineindium-bis-(cyclopentadienyl) zirconium dichloride;

[0365] N,N′-diisopropyl-3-phenyl-1,3-diketimineindium-bis-(cyclopentadienyl) zirconium dimethyl;

[0366] N,N′-diisopropyl-3-phenyl-1,3-diketimineindium-bis-(cyclopentadienyl) zirconium 2-(N,N-dimethylamino)benzyl;

[0367] N,N′-diisopropyl-3-phenyl-1,3-diketimineindium-bis-(cyclopentadienyl) zirconium 1,diphenyl-1,3-butadiene;

[0368] N,N′-diisopropyl-3-phenyl-1,3-diketimineindium-bis-(n-butylcyclopentadienyl) zirconium dichloride;

[0369] N,N′-diisopropyl-3-phenyl-1,3-diketimineindium-bis-(n-butylcyclopentadienyl) zirconium dimethyl;

[0370] N,N′-diisopropyl-3-phenyl-1,3-diketimineindium-bis-(n-butylcyclopentadienyl) zirconium2-(N,N-dimethylamino)benzyl;

[0371] N,N′-diisopropyl-3-phenyl-1,3-diketimineindium-bis-(n-butylcyclopentadienyl) zirconium 1,diphenyl-1,3-butadiene;

[0372] N,N′-diisopropyl-3-phenyl-1,3-diketimine indium-bis-(inden-1-yl)zirconium dichloride;

[0373] N,N′-diisopropyl-3-phenyl-1,3-diketimine indium-bis-(inden-1-yl)zirconium dimethyl;

[0374] N,N′-diisopropyl-3-phenyl-1,3-diketimine indium-bis-(inden-1-yl)zirconium 2-(N,N-dimethylamino)benzyl;

[0375] N,N′-diisopropyl-3-phenyl-1,3-diketimine indium-bis-(inden-1-yl)zirconium 1,diphenyl-1,3-butadiene;

[0376] N,N′-diisopropyl-3-phenyl-1,3-diketimineindium-bis-(2-methyl-4-phenylinden-1-yl) zirconium dichloride;

[0377] N,N′-diisopropyl-3-phenyl-1,3-diketimineindium-bis-(2-methyl-4-phenylinden-1-yl) zirconium dimethyl;

[0378] N,N′-diisopropyl-3-phenyl-1,3-diketimineindium-bis-(2-methyl-4-phenylinden-1-yl) zirconium2-(N,N-dimethylamino)benzyl;

[0379] N,N′-diisopropyl-3-phenyl-1,3-diketimineindium-bis-(2-methyl-4-phenylinden-1-yl) zirconium1,diphenyl-1,3-butadiene;

[0380] N,N′-diisopropyl-3-phenyl-1,3-diketimineindium-bis-(3-(1-pyrrolidinyl)inden-1-yl) zirconium dichloride;

[0381] N,N′-diisopropyl-3-phenyl-1,3-diketimineindium-bis-(3-(1-pyrrolidinyl)inden-1-yl) zirconium dimethyl;

[0382] N,N′-diisopropyl-3-phenyl-1,3-diketimineindium-bis-(3-(1-pyrrolidinyl)inden-1-yl) zirconium2-(N,N-dimethylamino)benzyl;

[0383] N,N′-diisopropyl-3-phenyl-1,3-diketimineindium-bis-(3-(1-pyrrolidinyl)inden-1-yl) zirconium1,diphenyl-1,3-butadiene;

[0384] N,N′-diisopropyl-dimethylguanidinateindium-bis-(cyclopentadienyl) zirconium dichloride;

[0385] N,N′-diisopropyl-dimethylguanidinateindium-bis-(cyclopentadienyl) zirconium dimethyl;

[0386] N,N′-diisopropyl-dimethylguanidinateindium-bis-(cyclopentadienyl) zirconium 2-(N,N-dimethylamino)benzyl;

[0387] N,N′-diisopropyl-dimethylguanidinateindium-bis-(cyclopentadienyl) zirconium 1,diphenyl-1,3-butadiene;

[0388] N,N′-diisopropyl-dimethylguanidinateindium-bis-(n-butylcyclopentadienyl) zirconium dichloride;

[0389] N,N′-diisopropyl-dimethylguanidinateindium-bis-(n-butylcyclopentadienyl) zirconium dimethyl;

[0390] N,N′-diisopropyl-dimethylguanidinateindium-bis-(n-butylcyclopentadienyl) zirconium2-(N,N-dimethylamino)benzyl;

[0391] N,N′-diisopropyl-dimethylguanidinateindium-bis-(n-butylcyclopentadienyl) zirconium 1,diphenyl-1,3-butadiene;

[0392] N,N′-diisopropyl-dimethylguanidinate indium-bis-(inden-1-yl)zirconium dichloride;

[0393] N,N′-diisopropyl-dimethylguanidinate indium-bis-(inden-1-yl)zirconium dimethyl;

[0394] N,N′-diisopropyl-dimethylguanidinate indium-bis-(inden-1-yl)zirconium 2-(N,N-dimethylamino)benzyl;

[0395] N,N′-diisopropyl-dimethylguanidinate indium-bis-(inden-1-yl)zirconium 1,diphenyl-1,3-butadiene;

[0396] N,N′-diisopropyl-dimethylguanidinateindium-bis-(2-methyl-4-phenylinden-1-yl) zirconium dichloride;

[0397] N,N′-diisopropyl-dimethylguanidinateindium-bis-(2-methyl-4-phenylinden-1-yl) zirconium dimethyl;

[0398] N,N′-diisopropyl-dimethylguanidinateindium-bis-(2-methyl-4-phenylinden-1-yl) zirconium2-(N,N-dimethylamino)benzyl;

[0399] N,N′-diisopropyl-dimethylguanidinateindium-bis-(2-methyl-4-phenylinden-1-yl) zirconium1,diphenyl-1,3-butadiene;

[0400] N,N′-diisopropyl-dimethylguanidinateindium-bis-(3-(1-pyrrolidinyl)inden-1-yl) zirconium dichloride;

[0401] N,N′-diisopropyl-dimethylguanidinateindium-bis-(3-(1-pyrrolidinyl)inden-1-yl) zirconium dimethyl;

[0402] N,N′-diisopropyl-dimethylguanidinateindium-bis-(3-(1-pyrrolidinyl)inden-1-yl) zirconium2-(N,N-dimethylamino)benzyl;

[0403] N,N′-diisopropyl-dimethylguanidinateindium-bis-(3-(1-pyrrolidinyl)inden-1-yl) zirconium1,diphenyl-1,3-butadiene;

[0404] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinateindium-bis-(cyclopentadienyl)zirconium dichloride;

[0405] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinateindium-bis-(cyclopentadienyl)zirconium dimethyl;

[0406] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinateindium-bis-(cyclopentadienyl)zirconium 2-(N,N-dimethylamino)benzyl;

[0407] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinateindium-bis-(cyclopentadienyl)zirconium 1,diphenyl-1,3-butadiene;

[0408] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinateindium-bis-(n-butylcyclopentadienyl) zirconium dichloride;

[0409] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinateindium-bis-(n-butylcyclopentadienyl) zirconium dimethyl;

[0410] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinateindium-bis-(n-butylcyclopentadienyl) zirconium2-(N,N-dimethylamino)benzyl;

[0411] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinateindium-bis-(n-butylcyclopentadienyl) zirconium 1,diphenyl-1,3-butadiene;

[0412] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinateindium-bis-(inden-1-yl) zirconium dichloride;

[0413] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinateindium-bis-(inden-1-yl) zirconium dimethyl;

[0414] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinateindium-bis-(inden-1-yl) zirconium 2-(N,N-dimethylamino)benzyl;

[0415] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinateindium-bis-(inden-1-yl) zirconium 1,diphenyl-1,3-butadiene;

[0416] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinateindium-bis-(2-methyl-4-phenylinden-1-yl) zirconium dichloride;

[0417] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinateindium-bis-(2-methyl-4-phenylinden-1-yl) zirconium dimethyl;

[0418] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinateindium-bis-(2-methyl-4-phenylinden-1-yl) zirconium2-(N,N-dimethylamino)benzyl;

[0419] 1,3,4,6,7,8-hexahydro-pyrimido [1,2-a] pyrimidinateindium-bis-(2-methyl-4-phenylinden-1-yl) zirconium1,diphenyl-1,3-butadiene;

[0420] 1,3,4,6,7,8-hexahydro-pyrimido [1,2-al pyrimidinateindium-bis-(3-(1-pyrrolidinyl)inden-1-yl) zirconium dichloride;

[0421] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinateindium-bis-(3-(1-pyrrolidinyl)inden-1-yl) zirconium dimethyl;

[0422] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinateindium-bis-(3-(1-pyrrolidinyl)inden-1-yl) zirconium2-(N,N-dimethylamino)benzyl; and

[0423] 1,3,4,6,7,8-hexahydro-pyrimido[1,2-a] pyrimidinateindium-bis-(3-(1-pyrrolidinyl)inden-1-yl) zirconium1,diphenyl-1,3-butadiene;

[0424] The skilled artisan will recognize that additional members of theforegoing list, obtainable by substitution of known ligands or differentGroup 4 metals for those specifically named are also included within theinvention. Moreover, it should also be recognized that all possibleelectronic distributions within the molecule, such as η³, η⁴ or η⁵ areintended to be included by the foregoing named compounds.

[0425] In general the complexes of the current invention can be preparedby first converting the ligands represented in formula 1a to a dianionicsalt (where R⁴ is H) via reaction with a metal amide such as sodiumbis(trimethylsilyl)amide or lithium bis(trimethylsilyl)amide. Thedianionic ligand derivative is then reacted with a metal complexprecursor such as MY³ ₄, MY³ ₃, or MY³ ₂ (and the corresponding Lewisbase adducts), where Y³ is defined as above. Alternatively, reactionsemploying the neutral ligand, where R⁴ is hydrogen, in combination withthe metal precursors M(NR³ ₂)₄ or MR³ ₄ can be employed. (Preparation ofthe ligands of formula 2a where Y^(1′) and Y^(2′) are each an NR¹ groupcan be readily accomplished by contacting a dimetaltetrahydrocarbyloxide compound of the formula ((R⁷O)₂Z)₂, where R⁷ isC₁₋₁₀ hydrocarbyl, or two R⁷ groups together are C₂₋₂₀ dihydrocarbyl,especially bis(catecholato)digallium with an alkali metal C₁₋₄dihydrocarbylamide, especially lithium dimethylamide.) All of theforegoing reactions are conducted in an inert solvent such as ahydrocarbon solvent or an etheral solvent in the temperature range of−100° C. to 150° C.

[0426] An especially useful metal complex precursor reagent correspondsto the formula 3:

[0427] wherein M is zirconium, R⁶ and LB are as previously defined andY³ each occurrence is chloride. Employment of this precursor in thereaction with ligands of this invention renders the resulting metalcomplex in high racemic purity, which is especially useful in thestereospecific polymerization of α-olefins.

[0428] Alternatively, where R⁴ in structures of formula 1a and 2a is atrimethylsilyl group the ligand can be reacted directly with any of theabove metal complex precursors of formula 3, employing similar reactionconditions.

[0429] The recovery of the desired Group 4 transition metal complex isaccomplished by separation of the product from any alkali metal oralkaline earth metal salts and devolatilization of the reaction medium.Extraction into a secondary solvent may be employed if desired.Alternatively, if the desired product is an insoluble precipitate,filtration or other separation techniques may be employed. Finalpurification, if required, may be accomplished by recrystallization froman inert solvent, employing low temperatures if needed.

[0430] The complexes are rendered catalytically active by combinationwith an activating cocatalyst or use of an activating technique, such asthose that are previously known in the art for use with Group 4 metalolefin polymerization complexes. Suitable activating cocatalysts for useherein include polymeric or oligomeric alumoxanes, especiallymethylalumoxane, triisobutyl aluminum modified methylalumoxane, orisobutylalumoxane; neutral Lewis acids, such as C₁₋₃₀ hydrocarbylsubstituted Group 13 compounds, especially tri(hydrocarbyl)aluminum- ortri(hydrocarbyl)boron compounds and halogenated (includingperhalogenated) derivatives thereof, having from 1 to 10 carbons in eachhydrocarbyl or halogenated hydrocarbyl group, more especiallyperfluorinated tri(aryl)boron compounds, and most especiallytris(pentafluoro-phenyl)borane; nonpolymeric, compatible,noncoordinating, ion forming compounds (including the use of suchcompounds under oxidizing conditions), especially the use of ammonium-,phosphonium-, oxonium-, carbonium-, silylium- or sulfonium-salts ofcompatible, noncoordinating anions, or ferrocenium salts of compatible,noncoordinating anions; bulk electrolysis (explained in more detailhereinafter); and combinations of the foregoing activating cocatalystsand techniques. The foregoing activating cocatalysts and activatingtechniques have been previously taught with respect to different metalcomplexes in the following references: EP-A-277,003, U.S. Pat. Nos.5,153,157, 5,064,802, 5,321,106, 5,721,185, 5,350,723, 5,425,872,5,625,087, 5,883,204, 5,919,983, 5,783,512, WO 99/15534, and U.S. Ser.No. 09/251,664, filed Feb. 17, 1999.

[0431] Combinations of neutral Lewis acids, especially the combinationof a trialkylaluminum compound having from 1 to 4 carbons in each alkylgroup and a halogenated tri(hydrocarbyl)boron compound having from 1 to20 carbons in each hydrocarbyl group, especiallytris(pentafluorophenyl)borane, further combinations of such neutralLewis acid mixtures with a polymeric or oligomeric alumoxane, andcombinations of a single neutral Lewis acid, especiallytris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxaneare especially desirable activating cocatalysts. Preferred molar ratiosof Group 4 metal complex:tris(pentafluoro-phenylborane:alumoxane arefrom 1:1:1 to 1:10:30, more preferably from 1:1:1.5 to 1:5:10.

[0432] Suitable ion forming compounds useful as cocatalysts in oneembodiment of the present invention comprise a cation which is aBronsted acid capable of donating a proton, and a compatible,noncoordinating anion, A⁻. As used herein, the term “noncoordinating”means an anion or substance which either does not coordinate to theGroup 4 metal containing precursor complex and the catalytic derivativederived therefrom, or which is only weakly coordinated to such complexesthereby remaining sufficiently labile to be displaced by a neutral Lewisbase. A noncoordinating anion specifically refers to an anion which whenfunctioning as a charge balancing anion in a cationic metal complex doesnot transfer an anionic substituent or fragment thereof to said cationthereby forming neutral complexes. “Compatible anions” are anions whichare not degraded to neutrality when the initially formed complexdecomposes and are noninterfering with desired subsequent polymerizationor other uses of the complex.

[0433] Preferred anions are those containing a single coordinationcomplex comprising a charge-bearing metal or metalloid core which anionis capable of balancing the charge of the active catalyst species (themetal cation) which may be formed when the two components are combined.Also, said anion should be sufficiently labile to be displaced byolefinic, diolefinic and acetylenically unsaturated compounds or otherneutral Lewis bases such as ethers or nitriles. Suitable metals include,but are not limited to, aluminum, gallium, niobium or tantalum. Suitablemetalloids include, but are not limited to, boron, phosphorus, andsilicon. Compounds containing anions which comprise coordinationcomplexes containing a single metal or metalloid atom are, of course,well known and many, particularly such compounds containing a singleboron atom in the anion portion, are available commercially.

[0434] Preferably such cocatalysts may be represented by the followinggeneral formula:

(L*-H)_(d) ⁺(A)^(d−)

[0435] wherein:

[0436] L* is a neutral Lewis base;

[0437] (L*-H)⁺ is a conjugate Bronsted acid of L*;

[0438] A^(d−) is a noncoordinating, compatible anion having a charge ofd−, and

[0439] d is an integer from 1 to 3.

[0440] More preferably A^(d−) corresponds to the formula: [M′Q₄]⁻;

[0441] wherein:

[0442] M′ is boron or aluminum in the +3 formal oxidation state; and

[0443] Q independently each occurrence is selected from hydride,dialkylamido, halide, hydrocarbyl, hydrocarbyloxide, halo-substitutedhydrocarbyl, halo-substituted hydrocarbyloxy, and halo-substitutedsilylhydrocarbyl radicals (including perhalogenatedhydrocarbyl-perhalogenated hydrocarbyloxy- and perhalogenatedsilylhydrocarbyl radicals), said Q having up to 20 carbons with theproviso that in not more than one occurrence is Q halide. Examples ofsuitable hydrocarbyloxide Q groups are disclosed in U.S. Pat. No.5,296,433.

[0444] In a more preferred embodiment, d is one, that is, the counterion has a single negative charge and is A⁻. Activating cocatalystscomprising boron which are particularly useful in the preparation ofcatalysts of this invention may be represented by the following generalformula:

(L*-H)⁺(BQ₄)⁻;

[0445] wherein:

[0446] L* is as previously defined;

[0447] B is boron in a formal oxidation state of 3; and

[0448] Q is a hydrocarbyl-, hydrocarbyloxy-, fluorohydrocarbyl-,fluorohydrocarbyloxy-, hydroxyfluorohydrocarbyl-,dihydrocarbylaluminumoxyfluorohydrocarbyl-, or fluorinatedsilylhydrocarbyl-group of up to 20 nonhydrogen atoms, with the provisothat in not more than one occasion is Q hydrocarbyl. Most preferably, Qis each occurrence a fluorinated aryl group, especially, apentafluorophenyl group.

[0449] Preferred Lewis base salts are ammonium salts, more preferablytrialkylammonium salts containing one or more C₁₂₋₄₀ alkyl groups.

[0450] Illustrative, but not limiting, examples of boron compounds whichmay be used as an activating cocatalyst in the preparation of theimproved catalysts of this invention are

[0451] tri-substituted ammonium salts such as:

[0452] trimethylammonium tetrakis(pentafluorophenyl) borate,

[0453] triethylammonium tetrakis(pentafluorophenyl) borate,

[0454] tripropylammonium tetrakis(pentafluorophenyl) borate,

[0455] tri(n-butyl)ammonium tetrakis(pentafluorophenyl) borate,

[0456] tri(sec-butyl)ammonium tetrakis(pentafluorophenyl) borate,

[0457] N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate,

[0458] N,N-dimethylanilinium n-butyltris(pentafluorophenyl) borate,

[0459] N,N-dimethylanilinium benzyltris(pentafluorophenyl) borate,

[0460] N,N-dimethylaniliniumtetrakis(4-(t-butyldimethylsilyl)-2,3,5,6-tetrafluorophenyl) borate,

[0461] N,N-dimethylaniliniumtetrakis(4-(triisopropylsilyl)-2,3,5,6-tetrafluorophenyl) borate,

[0462] N,N-dimethylanilinium pentafluorophenoxytris(pentafluorophenyl)borate,

[0463] N,N-diethylanilinium tetrakis(pentafluorophenyl) borate,

[0464] N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(pentafluorophenyl)borate,

[0465] dimethyltetradecylammonium tetrakis(pentafluorophenyl) borate,

[0466] dimethylhexadecylammonium tetrakis(pentafluorophenyl) borate,

[0467] dimethyloctadecylammonium tetrakis(pentafluorophenyl) borate,

[0468] methylditetradecylammonium tetrakis(pentafluorophenyl) borate,

[0469] methylditetradecylammonium (hydroxyphenyl)tris(pentafluorophenyl)borate,

[0470] methylditetradecylammonium(diethylaluminoxyphenyl)tris(pentafluorophenyl) borate,

[0471] methyldihexadecylammonium tetrakis(pentafluorophenyl) borate,

[0472] methyldihexadecylammonium (hydroxyphenyl)tris(pentafluorophenyl)borate,

[0473] methyldihexadecylammonium(diethylaluminoxyphenyl)tris(pentafluorophenyl) borate,

[0474] methyldioctadecylammonium tetrakis(pentafluorophenyl) borate,

[0475] methyldioctadecylammonium (hydroxyphenyl)tris(pentafluorophenyl)borate,

[0476] methyldioctadecylammonium(diethylaluminoxyphenyl)tris(pentafluorophenyl) borate, mixtures of theforegoing,

[0477] dialkyl ammonium salts such as:

[0478] di-(i-propyl)ammonium tetrakis(pentafluorophenyl) borate,

[0479] methyloctadecylammonium tetrakis(pentafluorophenyl) borate,

[0480] methyloctadodecylammonium tetrakis(pentafluorophenyl) borate, and

[0481] dioctadecylammonium tetrakis(pentafluorophenyl) borate;

[0482] tri-substituted phosphonium salts such as:

[0483] triphenylphosphonium tetrakis(pentafluorophenyl) borate,

[0484] methyldioctadecylphosphonium tetrakis(pentafluorophenyl) borate,and

[0485] tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate;

[0486] di-substituted oxonium salts such as:

[0487] diphenyloxonium tetrakis(pentafluorophenyl) borate,

[0488] di(o-tolyl)oxonium tetrakis(pentafluorophenyl) borate, and

[0489] di(octadecyl)oxonium tetrakis(pentafluorophenyl) borate;

[0490] di-substituted sulfonium salts such as:

[0491] di(o-tolyl)sulfonium tetrakis(pentafluorophenyl) borate, and

[0492] methylcotadecylsulfonium tetrakis(pentafluorophenyl) borate.

[0493] Preferred (L*-H)⁺ cations are methyldioctadecylammonium anddimethyloctadecylammonium. The use of the above Bronsted acid salts asactivating cocatalysts for addition polymerization catalysts is known inthe art, having been disclosed in U.S. Pat. Nos. 5,064,802, 5,919,983,5,783,512 and elsewhere.

[0494] Another suitable ion forming, activating cocatalyst comprises asalt of a cationic oxidizing agent and a noncoordinating, compatibleanion represented by the formula:

(Ox^(e+))_(d)(A^(d−))_(e).

[0495] wherein:

[0496] Ox^(e+) is a cationic oxidizing agent having a charge of e+;

[0497] e is an integer from 1 to 3; and

[0498] A^(d−) and d are as previously defined.

[0499] Examples of cationic oxidizing agents include: ferrocenium,hydrocarbyl-substituted ferrocenium, Ag^(+,) or Pb⁺². Preferredembodiments of A^(d−) are those anions previously defined with respectto the Bronsted acid containing activating cocatalysts, especiallytetrakis(pentafluorophenyl)borate. The use of the above salts asactivating cocatalysts for addition polymerization catalysts is known inthe art, having been disclosed in U.S. Pat. No. 5,321,106.

[0500] Another suitable ion forming, activating cocatalyst comprises acompound which is a salt of a carbenium ion and a noncoordinating,compatible anion represented by the formula:

{circle over (C)}⁺+A⁻

[0501] wherein:

[0502] {circle over (C)}⁺ is a C₁₋₂₀ carbenium ion; and

[0503] A⁻ is as previously defined. A preferred carbenium ion is thetrityl cation, that is triphenylmethylium. The use of the abovecarbenium salts as activating cocatalysts for addition polymerizationcatalysts is known in the art, having been disclosed in U.S. Pat. No.5,350,723.

[0504] A further suitable ion forming, activating cocatalyst comprises acompound which is a salt of a silylium ion and a noncoordinating,compatible anion represented by the formula:

R₃Si(X′)_(q) ⁺A⁻

[0505] wherein:

[0506] R is C₁₋₁₀ hydrocarbyl, and X′, q and A⁻ are as previouslydefined.

[0507] Preferred silylium salt activating cocatalysts aretrimethylsilylium tetrakispentafluorophenylborate, triethylsilyliumtetrakispentafluorophenylborate and ether substituted adducts thereof.The use of the above silylium salts as activating cocatalysts foraddition polymerization catalysts is known in the art, having beendisclosed in U.S. Pat. No. 5,625,087.

[0508] Certain complexes of alcohols, mercaptans, silanols, and oximeswith tris(pentafluorophenyl)borane are also effective catalystactivators and may be used according to the present invention. Suchcocatalysts are disclosed in U.S. Pat. No. 5,296,433.

[0509] Another class of suitable catalyst activators are expandedanionic compounds corresponding to the formula: (A^(1+a) ¹ )_(b) _(²)(Z¹J¹ _(j) _(¹) )^(−c1) _(d) _(¹) ,

[0510] wherein:

[0511] A¹ is a cation of charge +a¹,

[0512] Z¹ is an anion group of from 1 to 50, preferably 1 to 30 atoms,not counting hydrogen atoms, further containing two or more Lewis basesites;

[0513] J¹ independently each occurrence is a Lewis acid coordinated toat least one Lewis base site of Z¹, and optionally two or more such J¹groups may be joined together in a moiety having multiple Lewis acidicfunctionality,

[0514] j¹ is a number from 2 to 12 and

[0515] a¹, b¹, c¹, and d¹ are integers from 1 to 3, with the provisothat a¹×b¹ is equal to c¹×d¹.

[0516] The foregoing cocatalysts (illustrated by those havingimidazolide, substituted imidazolide, imidazolinide, substitutedimidazolinide, benzimidazolide, or substituted benzimidazolide anions)may be depicted schematically as follows:

[0517] wherein:

[0518] A¹⁺ is a monovalent cation as previously defined, and preferablyis a trihydrocarbyl ammonium cation, containing one or two C₁₀₋₄₀ alkylgroups, especially the methylbis(tetradecyl)ammonium- ormethylbis(octadecyl)ammonium-cation,

[0519] R⁸, independently each occurrence, is hydrogen or a halo,hydrocarbyl, halocarbyl, halohydrocarbyl, silylhydrocarbyl, or silyl,(including mono-, di- and tri(hydrocarbyl)silyl) group of up to 30 atomsnot counting hydrogen, preferably C₁₋₂₀ alkyl, and

[0520] J¹ is tris(pentafluorophenyl)borane ortris(pentafluorophenyl)aluminane.

[0521] Examples of these catalyst activators include thetrihydrocarbylammonium-, especially, methylbis(tetradecyl)ammonium- ormethylbis(octadecyl)ammonium-salts of:

[0522] bis(tris(pentafluorophenyl)borane)imidazolide,

[0523] bis(tris(pentafluorophenyl)borane)-2-undecylimidazolide,bis(tris(pentafluorophenyl)borane)-

[0524] 2-heptadecylimidazolide,bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolide,

[0525]bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolide,

[0526] bis(tris(pentafluorophenyl)borane)imidazolinide,

[0527] bis(tris(pentafluorophenyl)borane)-2-undecylimidazolinide,

[0528] bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolinide,

[0529] bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolinide,

[0530]bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolinide,

[0531] bis(tris(pentafluorophenyl)borane)-5,6-dimethylbenzimidazolide,

[0532]bis(tris(pentafluorophenyl)borane)-5,6-bis(undecyl)benzimidazolide,

[0533] bis(tris(pentafluorophenyl)alumane)imidazolide,

[0534] bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolide,

[0535] bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolide,

[0536] bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolide,

[0537]bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolide,

[0538] bis(tris(pentafluorophenyl)alumane)imidazolinide,

[0539] bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolinide,

[0540] bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolinide,

[0541]bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolinide,

[0542]bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolinide,

[0543] bis(tris(pentafluorophenyl)alumane)-5,6-dimethylbenzimidazolide,and

[0544]bis(tris(pentafluorophenyl)alumane)-5,6-bis(undecyl)benzimidazolide.

[0545] A further class of suitable activating cocatalysts includecationic Group 13 salts corresponding to the formula:

[M″Q¹ ₂L′_(1′)]⁺(Ar^(f) ₃M′Q²)⁻

[0546] wherein:

[0547] M″ is aluminum, gallium, or indium;

[0548] M′ is boron or aluminum;

[0549] Q¹ is C₁₋₂₀ hydrocarbyl, optionally substituted with one or moregroups which independently each occurrence are hydrocarbyloxy,hydrocarbylsiloxy, hydrocarbylsilylamino, di(hydrocarbylsilyl)amino,hydrocarbylamino, di(hydrocarbyl)amino, di(hydrocarbyl)phosphino, orhydrocarbylsulfido groups having from 1 to 20 atoms other than hydrogen,or, optionally, two or more Q¹ groups may be covalently linked with eachother to form one or more fused rings or ring systems;

[0550] Q² is an alkyl group, optionally substituted with one or morecycloalkyl or aryl groups, said Q² having from 1 to 30 carbons;

[0551] L′ is a monodentate or polydentate Lewis base, preferably L′ isreversibly coordinated to the metal complex such that it may bedisplaced by an olefin monomer, more preferably L′ is a monodentateLewis base;

[0552] 1′ is a number greater than zero indicating the number of Lewisbase moieties, L′, and

[0553] Ar^(f) independently each occurrence is an anionic ligand group;preferably Ar^(f) is selected from the group consisting of halide, C₁₋₂₀halohydrocarbyl, and Q¹ ligand groups, more preferably Ar^(f) is afluorinated hydrocarbyl moiety of from 1 to 30 carbon atoms, mostpreferably Ar^(f) is a fluorinated aromatic hydrocarbyl moiety of from 6to 30 carbon atoms, and most highly preferably Ar^(f) is aperfluorinated aromatic hydrocarbyl moiety of from 6 to 30 carbon atoms.

[0554] Examples of the foregoing Group 13 metal salts are alumiciniumtris(fluoroaryl)borates or gallicinium tris(fluoroaryl)boratescorresponding to the formula:

[M″Q¹ ₂L′_(1′)]⁺(Ar^(f) ₃BQ²)⁻,

[0555] wherein M″ is aluminum or gallium; Q¹ is C₁₋₂₀ hydrocarbyl,preferably C₁₋₈ alkyl; Ar^(f) is perfluoroaryl, preferablypentafluorophenyl; and Q² is C₁₋₈ alkyl, preferably C₁₋₈ alkyl. Morepreferably, Q¹ and Q² are identical C₁₋₈ alkyl groups, most preferably,methyl, ethyl or octyl.

[0556] The foregoing activating cocatalysts may also be used incombination. An especially preferred combination is a mixture of atri(hydrocarbyl)aluminum or tri(hydrocarbyl)borane compound having from1 to 4 carbons in each hydrocarbyl group or an ammonium borate with anoligomeric or polymeric alumoxane compound.

[0557] The molar ratio of catalyst/cocatalyst employed preferably rangesfrom 1:10,000 to 100:1, more preferably from 1:5000 to 10:1, mostpreferably from 1:1000 to 1:1. Alumoxane, when used by itself as anactivating cocatalyst, is employed in large quantity, generally at least100 times the quantity of metal complex on a molar basis.Tris(pentafluorophenyl)borane, where used as an activating cocatalyst isemployed in a molar ratio to the metal complex of form 0.5:1 to 10:1,more preferably from 1:1 to 6:1 most preferably from 1:1 to 5:1. Theremaining activating cocatalysts are generally employed in approximatelyequimolar quantity with the metal complex.

[0558] The catalysts, whether or not supported in any suitable manner,may be used to polymerize ethylenically unsaturated monomers having from2 to 100,000 carbon atoms either alone or in combination. Preferredaddition polymerizable monomers for use herein include olefins,diolefins and mixtures thereof. Preferred olefins are aliphatic oraromatic compounds containing vinylic unsaturation as well as cycliccompounds containing ethylenic unsaturation. Examples of the latterinclude cyclobutene, cyclopentene, norbornene, and norbornenederivatives that are substituted in the 5- and 6-positions with C₁₋₂₀hydrocarbyl groups. Preferred diolefins are C₄₋₄₀ diolefin compounds,including ethylidene norbornene, 1,4-hexadiene, norbornadiene, and thelike. The catalysts and processes herein are especially suited for usein preparation of ethylene/1-butene, ethylene/1-hexene,ethylene/styrene, ethylene/propylene, ethylene/1-pentene,ethylene/4-methyl-1-pentene and ethylene/1-octene copolymers as well asterpolymers of ethylene, propylene and a nonconjugated diene, such as,for example, EPDM terpolymers.

[0559] Most preferred monomers include the C₂₋₂₀ α-olefins, especiallyethylene, propylene, isobutylene, 1-butene, 1-pentene, 1-hexene,3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene, long chainmacromolecular α-olefins, and mixtures thereof. Other preferred monomersinclude styrene, C₁₋₄ alkyl substituted styrene, ethylidenenorbornene,1,4-hexadiene, 1,7-octadiene, vinylcyclohexane, 4-vinylcyclohexene,divinylbenzene, and mixtures thereof with ethylene. Long chainmacromolecular α-olefins are vinyl terminated polymeric remnants formedin situ during continuous solution polymerization reactions. Undersuitable processing conditions such long chain macromolecular units arereadily polymerized into the polymer product along with ethylene andother short chain olefin monomers to give small quantities of long chainbranching in the resulting polymer.

[0560] Preferred monomers include a combination of ethylene and one ormore comonomers selected from monovinyl aromatic monomers,4-vinylcyclohexene, vinylcyclohexane, norbornadiene,ethylidene-norbornene, C₃₋₁₀ aliphatic α-olefins (especially propylene,isobutylene, 1-butene, 1-hexene, 3-methyl-1-pentene, 4-methyl-1-pentene,and 1-octene), and C₄₋₄₀ dienes. Most preferred monomers are mixtures ofethylene and styrene; mixtures of ethylene, propylene and styrene;mixtures of ethylene, styrene and a nonconjugated diene, especiallyethylidenenorbornene or 1,4-hexadiene, and mixtures of ethylene,propylene and a nonconjugated diene, especially ethylidenenorbornene or1,4-hexadiene.

[0561] In general, the polymerization may be accomplished at conditionswell known in the prior art for Ziegler-Natta or Kaminsky-Sinn typepolymerization reactions, that is, temperatures from 0-250° C.,preferably 30 to 200° C. and pressures from atmospheric to 10,000atmospheres. Suspension, solution, slurry, gas phase, solid state powderpolymerization or other process condition may be employed if desired. Asupport, especially silica, alumina, or a polymer (especiallypoly(tetrafluoroethylene) or a polyolefin) may be employed, anddesirably is employed when the catalysts are used in a gas phasepolymerization process. The support is preferably employed in an amountto provide a weight ratio of catalyst (based on metal):support from1:10⁶ to 1:10³, more preferably from 1:10⁶to 1:10⁴.

[0562] In most polymerization reactions the molar ratio ofcatalyst:polymerizable compounds employed is from 10⁻¹²:1 to 10³¹ ¹:1,more preferably from 10⁻⁹:1 to 10⁻⁵:1.

[0563] Suitable solvents use for solution polymerization are liquidsthat are substantially inert under process conditions encountered intheir usage. Examples include straight and branched-chain hydrocarbonssuch as isobutane, butane, pentane, hexane, heptane, octane, andmixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane,cycloheptane, methylcyclohexane, methylcycloheptane, and mixturesthereof; perfluorinated hydrocarbons such as perfluorinated C₄₋₁₀alkanes, and alkyl-substituted aromatic compounds such as benzene,toluene, xylene, and ethylbenzene. Suitable solvents also include liquidolefins which may act as monomers or comonomers.

[0564] The catalysts may be utilized in combination with at least oneadditional homogeneous or heterogeneous polymerization catalyst in thesame reactor or in separate reactors connected in series or in parallelto prepare polymer blends having desirable properties. An example ofsuch a process is disclosed in WO 94/00500.

[0565] The catalysts of the present invention are particularlyadvantageous for the production of ethylene homopolymers andethylene/α-olefin copolymers having high levels of long chain branching.The use of the catalysts of the present invention in continuouspolymerization processes, especially continuous, solution polymerizationprocesses, allows for elevated reactor temperatures which favor theformation of vinyl terminated polymer chains that may be incorporatedinto a growing polymer, thereby giving a long chain branch. The use ofthe present catalyst compositions advantageously allows for theeconomical production of ethylene/α-olefin copolymers havingprocessability similar to high pressure, free radical produced lowdensity polyethylene.

[0566] The present catalyst compositions may be advantageously employedto prepare olefin polymers having improved processing properties bypolymerizing ethylene alone or ethylene/α-olefin mixtures with lowlevels of a “H” branch inducing diene, such as norbornadiene,1,7-octadiene, or 1,9-decadiene. The unique combination of elevatedreactor temperatures, high molecular weight (or low melt indices) athigh reactor temperatures and high comonomer reactivity advantageouslyallows for the economical production of polymers having excellentphysical properties and processability. Preferably such polymerscomprise ethylene, a C₃₋₂₀ α-olefin and a “H”-branching comonomer.Preferably, such polymers are produced in a solution process, mostpreferably a continuous solution process.

[0567] The catalyst composition may be prepared as a homogeneouscatalyst by addition of the requisite components to a solvent or diluentin which polymerization will be conducted. The catalyst composition mayalso be prepared and employed as a heterogeneous catalyst by adsorbing,depositing or chemically attaching the requisite components on aninorganic or organic particulated solid. Examples of such solidsinclude, silica, silica gel, alumina, clays, expanded clays (aerogels),aluminosilicates, trialkylaluminum compounds, and organic or inorganicpolymeric materials, especially polyolefins. In a preferred embodiment,a heterogeneous catalyst is prepared by reacting an inorganic compound,preferably a tri(C₁₋₄ alkyl)aluminum compound, with an activatingcocatalyst, especially an ammonium salt of ahydroxyaryl(trispentafluoro-phenyl)borate, such as an ammonium salt of(4-hydroxy-3,5-ditertiarybutylphenyl)tris-(pentafluorophenyl)borate or(4-hydroxyphenyl)-tris(pentafluorophenyl)borate. This activatingcocatalyst is deposited onto the support by coprecipitating, imbibing,spraying, or similar technique, and thereafter removing any solvent ordiluent. The metal complex is added to the support, also by adsorbing,depositing or chemically attaching the same to the support, eithersubsequently, simultaneously or prior to addition of the activatingcocatalyst.

[0568] When prepared in heterogeneous or supported form, the catalystcomposition is employed in a slurry or gas phase polymerization. As apractical limitation, slurry polymerization takes place in liquiddiluents in which the polymer product is substantially insoluble.Preferably, the diluent for slurry polymerization is one or morehydrocarbons with less than 5 carbon atoms. If desired, saturatedhydrocarbons such as ethane, propane or butane may be used in whole orpart as the diluent. Likewise, the a-olefin monomer or a mixture ofdifferent α-olefin monomers may be used in whole or part as the diluent.Most preferably, at least a major part of the diluent comprises theα-olefin monomer or monomers to be polymerized. A dispersant,particularly an elastomer, may be dissolved in the diluent utilizingtechniques known in the art, if desired.

[0569] At all times, the individual ingredients as well as the recoveredcatalyst components must be protected from oxygen and moisture.Therefore, the catalyst components and catalysts must be prepared andrecovered in an oxygen and moisture free atmosphere. Preferably,therefore, the reactions are performed in the presence of an dry, inertgas, such as, for example, nitrogen.

[0570] The polymerization may be carried out as a batchwise or acontinuous polymerization process. A continuous process is preferred, inwhich event catalyst, ethylene, comonomer, and optionally solvent, arecontinuously supplied to the reaction zone, and polymer productcontinuously removed therefrom.

[0571] Without limiting in any way the scope of the invention, one meansfor carrying out such a polymerization process is as follows: In astirred-tank reactor, the monomers to be polymerized are introducedcontinuously, together with solvent and an optional chain transferagent. The reactor contains a liquid phase composed substantially ofmonomers, together with any solvent or additional diluent and dissolvedpolymer. If desired, a small amount of a “H”-branch inducing diene suchas norbornadiene, 1,7-octadiene or 1,9-decadiene may also be added.Catalyst and cocatalyst are continuously introduced in the reactorliquid phase. The reactor temperature and pressure may be controlled byadjusting the solvent/monomer ratio, the catalyst addition rate, as wellas by cooling or heating coils, jackets or both. The polymerization rateis controlled by the rate of catalyst addition. The ethylene content ofthe polymer product is determined by the ratio of ethylene to comonomerin the reactor, which is controlled by manipulating the respective feedrates of these components to the reactor. The polymer product molecularweight is controlled, optionally, by controlling other polymerizationvariables such as the temperature, monomer concentration, or by thepreviously mention chain transfer agent, such as a stream of hydrogenintroduced to the reactor, as is well known in the art. The reactoreffluent is contacted with a catalyst kill agent such as water. Thepolymer solution is optionally heated, and the polymer product isrecovered by flashing off gaseous monomers as well as residual solventor diluent at reduced pressure, and, if necessary, conducting furtherdevolatilization in equipment such as a devolatilizing extruder. In acontinuous process the mean residence time of the catalyst and polymerin the reactor generally is from about 5 minutes to 8 hours, andpreferably from 10 minutes to 6 hours.

[0572] Ethylene homopolymers and ethylene/α-olefin copolymers areparticularly suited for preparation according to the invention.Generally such polymers have densities from 0.85 to 0.96 g/ml. Typicallythe molar ratio of α-olefin comonomer to ethylene used in thepolymerization may be varied in order to adjust the density of theresulting polymer. When producing materials with a density range of from0.91 to 0.93 the comonomer to monomer ratio is less than 0.2, preferablyless than 0.05, even more preferably less than 0.02, and may even beless than 0.01. In the above polymerization process hydrogen has beenfound to effectively control the molecular weight of the resultingpolymer. Typically, the molar ratio of hydrogen to monomer is less thanabout 0.5, preferably less than 0.2, more preferably less than 0.05,even more preferably less than 0.02 and may even be less than 0.01.

EXAMPLES

[0573] It is understood that the present invention is operable in theabsence of any component which has not been specifically disclosed. Thefollowing examples are provided in order to further illustrate theinvention and are not to be construed as limiting. Unless stated to thecontrary, all parts and percentages are expressed on a weight basis. Theterm “overnight”, if used, refers to a time of approximately 16-18hours, “room temperature”, if used, refers to a temperature of about20-25° C., and “mixed alkanes” refers to a mixture of hydrogenatedpropylene oligomers, mostly C₆-C₁₂ isoalkanes, available commerciallyunder the trademark Isopar E™ from Exxon Chemicals Inc.

[0574] All solvents were purified using the technique disclosed byPangborn et al, Organometallics, 15, 1518-1520, (1996). All compounds,solutions, and reactions were handled under an inert atmosphere (drybox). The ¹H (300 MHz) and ¹³C{H} NMR (75 MHz) spectra were recorded onVarian Mercury Vx and Inova 300 spectrometers. The ¹H and ¹³C NMRspectra are referenced to the residual solvent peaks and are reported inppm relative to tetramethylsilane. All J values are given in Hz.Tetrahydrofuran (THF), diethylether, toluene, and hexane were usedfollowing passage through double columns charged with activated aluminaand Q-5® catalyst. The compounds Ti(NMe₂)₄, 1,3-diisopropylcarbodiimide,t-butyllithium, and 2,6-diisopropylaniline were all used as purchasedfrom Aldrich. The compound B(C₆F₅)₃ was used as purchased from BoulderScientific. All syntheses were performed under dry nitrogen or argonatmospheres using a combination of glove box and high vacuum techniques.“HRMS”, refers to high resolution mass spectroscopy.

[0575] X-ray data were collected at 173 K on a Siemens SMART PLATFORMequipped with a CCD area detector and graphite monochromator utilizingMoKα radiation (λ=0.71073 Å). Cell parameters were refined using 8192reflections. A hemisphere of data (1381 frames) was collected using theco-scan method (0.3° frame width). The first 50 frames were remeasuredat the end of data collection to monitor instrument and crystalstability (maximum correction on I was <1 percent). Absorptioncorrections by integration were applied based on measured indexedcrystal faces.

[0576] The structure was solved by the Direct Methods in SHELXTL5™(available from Bruker-AXS, Madison, Wis., USA) and refined usingfull-matrix least squares. The non-H atoms were refined with anisotropicthermal parameters and all of the H atoms were calculated in idealizedpositions and refined riding on their parent atoms. In the final cycleof refinement, 5769 observed reflections with I>2σ(I) were used torefine 335 parameters and the resulting R₁ and wR₂ were 3.20 percent and8.15 percent, respectively. Refinement was done using F².

Example 1Bis(dimethylamido)bis(2,6-diisopropylanilide)-indium-t-butyl-N,N′-diisopropylamidinate-titanium

[0577]

[0578] Preparation of t-Butyl-N,N′-diisopropylamidinate, Lithium Salt

[0579] 1,3-Diisopropylcarbodiimide (7.000 g, 55.47 mmol) was stirred inhexane (50 mL) at 0° C. as excess t-BuLi (1.7 M solution in pentane) wasadded dropwise. This mixture was allowed to stir overnight at roomtemperature during which time a white precipitate formed. This mixturewas then filtered and the white solid washed with hexane and dried undervacuum and used without further purification or analysis (9.63 g, 91.2percent yield).

[0580] Preparation of Dicloroindium-t-butyl-N,N′-diisopropylamidinate

[0581] t-Butyl-N,N′-diisopropylamidinate, lithium salt (9.629 g, 50.61mmol) and indium trichloride (11.19 g, 50.61 mmol) were mixed togetherin diethylether (50 mL) at 0° C. and then allowed to stir overnight atroom temperature. After the reaction period the volatiles were removedand the residue extracted and filtered using hot toluene. The productwas highly insoluable. Following extraction and filtration, the residuewas recrystallized from boiling toluene resulting in the isolation ofthe desired product as a slightly pale yellow crystalline solid (8.990g, 48.1 percent yield).

[0582]¹H NMR (CD₂Cl₂): δ 1.18 (d, ³J_(HH)=6.0 Hz, 12 H), 1.46 (s, 9 H),4.38 (sept., ³J_(HH)=5.9 Hz, 2H)

[0583]¹³C{H} NMR (CD₂Cl₂): δ 26.69, 29.79, 47.75.

[0584] HRMS(EI): calculated for C₁₁H₂₃N₂InCl₂ m/z 368.0279, found368.0280.

[0585] Analysis: Calculated. for C₁₁H₂₃N₂InCl₂: C, 35.80; H, 6.28; N,7.59.

[0586] Found: C, 34.49; H, 5.81; N, 7.48

[0587] Preparation of 2,6-Diisopropylaniline, Lithium Salt

[0588] n-BuLi (56.40 mmol, 35.25 mL of 1.6 M solution in hexane) wasadded dropwise to a solution of 2,6-diisopropylaniline (10.00 g, 56.40mmol) in hexane (100 mL). This mixture was allowed to stir for 3 hoursduring which time a white precipitate formed. After the reaction periodthe mixture was filtered and the white salt washed with hexane and driedunder vacuum and used without further purification or analysis (9.988 g,96.7 percent yield).

[0589] Preparation ofBis(2,6-diisopropylanilide)-indium-t-butyl-N,N′-diisopropylamidinate

[0590] 2,6-Diisopropylaniline, lithium salt (2.880 g, 15.72 mmol) indiethylether (10 mL) was added dropwise to a slurry ofdicloroindium-t-butyl-N,N′-diisopropylamidinate (2.900 g, 7.86 mmol) indiethylether (50 mL) at 0° C. This mixture was then allowed to stirovernight at room temperature. After the reaction period the volatileswere removed under vacuum and the residue extracted and filtered usinghexane. Concentration of the filtrate and cooling to −10° C. overnightresulted in the isolation of the desired product as a pale yellowcrystalline solid (2.982 g, 58.3 percent yield).

[0591]¹H NMR (C₆D₆): δ 0.86 (d, ³J_(HH)=6.0 Hz, 12 H), 1.06 (s, 9 H),1.28 (d, ³J_(HH)=6.9 Hz, 24 H), 3.24 (sept., ³J_(HH)=6.6 Hz, 4 H), 3.48(s, 2 H), 3.93 (sept., ³J_(HH)=6.3 Hz, 2 H), 6.90 (t, ³J_(HH)=7.5 Hz,2H)7.13 (d, ³J_(HH)=2.4 Hz, 4H)

[0592]¹³C {H} NMR (C₆D₆): δ23.45, 26.59,28.98,29.80,46.38, 118.83,123.02,137.46, 148.52

[0593] HRMS(EI): calculated for C₃₅H₅₉N₄In m/z 650.3780, found 650.3752

[0594] Analysis: Calculated for C₃₄H₅₉N₄In: C, 63.94; H, 9.31; N, 8.77.Found: C, 63.83; H, 9.81; N, 8.64.

[0595] Preparation ofBis(dimethylamido)bis(2,6-diisopropylanilide)-indium-t-butyl-N,N′-diisopropylamidinate-titanium

[0596]Bis(2,6-diisopropylanilide)-indium-t-butyl-N,N′-diisopropylamidinate(1.000 g, 1.54 mmol) and Ti(NMe₂)₄ were heated together in benzene (20mL) at 60° C. for eight hours under a nitrogen bubbler. During this timethe flask was occaissionally evacuated and then back flushed with freshnitrogen. The reaction mixture was then placed under full vaccum toremove all volatiles. The mixture was then extracted and filtered usingtoluene. The toluene solution was then concentrated and placed in afreezer (−10° C.) overnight during which time the desired productprecipitated as a yellow crystalline solid (0.394 g, 32.6 percentyield).

[0597]¹H NMR (C₆D₆): δ 0.67 (d, ³J_(HH)=6.0 Hz, 12 H), 0.90 (s, 9 H),1.38 (br, 24 H), 3.24 (s, 12 H), 3.82 (sept., ³J_(HH)=6.2 Hz, 2 H).3.94(sept., ³J_(HH)=6.9 Hz, 4 H), 6.96 (t, ³J_(HH)=7.6 Hz, 2 H),7.18(d,3J_(HH)=7.8 Hz, 4H)

[0598]¹³C{H} NMR (C₆D₆): 624.6 (br), 25.74,28.38,29.46, 31.92,39.48,46.56,46.93, 120.09, 123.22, 138.59, 154.38, 174.86

[0599] HRMS(EI): calculated for C₃₉H₆₉N₆InTi m/z 784.4103, found784.4127

[0600] Analysis: Calculated for C₃₈H₆₉N₆InTi: C, 59.07; H, 9.00; N,10.88

[0601] Found: C, 60.18; H, 8.57; N, 10.85

[0602] Ethylene/Octene (E/O) Copolymerizations

[0603] All feeds were passed though columns of activated alumina andQ-5™ catalyst prior to introduction to the reactor. A stirred 2-literParr reactor was charged with about 740 g of Isopar-E™ solvent and 118 gof 1-octene comonomer. Hydrogen was added as a molecular weight controlagent by differential pressure expansion from a 75 mL addition tank at25 psi (170 kPa). The reactor contents were then heated to thepolymerization temperature of 140° C. and saturated with ethylene at 500psig (3.4 Mpa). Triisbutylaluminum (TIBA) was added to the reactor in amolar ratio based on metal complex of 50:1. The metal complex(Example 1) and cocatalyst (methylalumoxane (MAO) or triphenylcarboniumtetrakis(pentafluorophenyl)-borate (TCTB)) were mixed as dilute toluenesolutions and transferred to a catalyst addition tank and injected intothe reactor through a stainless steel transfer line. The polymerizationconditions were maintained for 15 minutes with ethylene added on demand.Heat was continually removed from the reaction with an internal coolingcoil. The resulting solution was removed from the reactor, quenched withisopropyl alcohol, and stabilized by the addition of 10 mL of a toluenesolution containing approximately 67 mg of a hindered phenol antioxidant(Irganox™ 1010 from Ciba Geigy Corporation) and approximately 133 mg ofa phosphorous stabilizer (Irgafos™ 168 from Ciba Geigy Corporation).Between polymerization runs a wash cycle was conducted in which 850 g ofmixed alkanes were added to the reactor which was then heated to 150° C.and then emptied of the heated solvent immediately prior to a newpolymerization run.

[0604] Propylene (P) Polymerizations

[0605] All feeds were passed though columns of activated alumina andQ-5™ catalyst prior to introduction to the reactor. A stirred 2-literjacketed Autoclave Engineer's Zipper-Clave™ reactor was charged withabout 625 g of Isopar-E solvent and about 150 g of propylene. Hydrogenwas added as a molecular weight control agent by differential pressureexpansion from a 75 mL addition tank (Δ50 psig, 350 kPa). The reactorwas heated to 70° C. and allowed to equilibrate. Triisbutylaluminum(TIBA) was added to the reactor in a molar ratio based on metal complexof 50:1. The metal complex (Example 1) and cocatalyst (methylalumoxane(MAO) were mixed as dilute toluene solutions and transferred to acatalyst addition tank and injected into the reactor through a stainlesssteel transfer line. Heat was continually removed from the reaction witha cooling coil in the jacket. The resulting mixture was removed from thereactor, quenched with isopropyl alcohol, and stabilized by the additionof 10 mL of a toluene solution containing approximately 67 mg of ahindered phenol antioxidant (Irganox™ 1010 from Ciba Geigy Corporation).

[0606] Polymers were recovered by drying for about 20 hours in a vacuumoven set at 140° C. High temperature gel permeation chromatography (GPC)analysis of polymer samples were carried out in 1,2,4-trichlorobenzeneat 135° C. on a Waters 150 C high temperature instrument. Apolystyrene/polyethylene or polystyrene/polypropylene universalcalibration was carried out using narrow molecular weight distributionpolystyrene standards. Results are contained in Table 1. TABLE 1 Cat./cocat. Temp. Efficiency Run Monomer Cocatalyst (μmoles) (° C.) (g/mg Ti)Mw/Mn 1 E/O MAO   1/1000 70 26 167,000/17,500 (9.54) 2 ″ ″ ″ ″ 27562,000/56,500 (9.95) 3 ″ TPTB 1/1 ″ 34  598,000/44,100 (13.56) 4 ″ TPTB″ 140  7 132,000/7,600 (17.4)  5 ″ MAO   1/1000 ″ 5 144,000/11,200(12.8) 6 P ″  1/500 70 8  87,600/12,200 (7.17)

1. A Group 4 transition metal complex corresponding to the followingformula:

wherein: M is titanium, zirconium, or hafnium in the +4, +3, or +2oxidation state; Y¹ and Y² are independently an anionic or neutral,cyclic or non-cyclic, π-bonded group, NR¹, PR¹; NR¹ ₂, PR¹, or(R**)₃—P═N—; R** is in one occurrence a covalent bond to Z and in allremaining occurrences a monovalent ligand selected from hydrogen,halogen, or C₁₋₁₀ hydrocarbyl, or two R** groups together form adivalent ligand, Z is gallium or indium; Q is a neutral, anionic ordianionic ligand group depending on the oxidation state of M; j is 1 or2 depending on the oxidation state of M and the electronic nature of Q;t is 1 or 2, and when t is 2 there is a direct Z—Z bond; T independentlyeach occurrence is: —OR¹, —SR¹, —NR¹ ₂, —PR¹ ₂, —N═CR¹ ₂, —N═PR¹ ₃,

R¹ is independently each occurrence hydrogen, a hydrocarbyl group, atri(hydrocarbyl)silyl group, or a tri(hydrocarbyl)silylhydrocarbylgroup, said R¹ groups containing up to 20 atoms not counting hydrogen;R⁵ is R¹ or —N(R¹)₂; and two R¹ groups together or one or more R¹ groupstogether with R⁵ may optionally be joined to form a ring structure.
 2. Ametal complex according to claim 1 corresponding to formulas 4, 5, 6 and7:

wherein M, Z, T, Q, t and j are as defined in claim 1; R² is hydrogen,or a hydrocarbyl, halohydrocarbyl, dihydrocarbylamino-hydrocarbyl,tri(hydrocarbylsilyl)hydrocarbyl, Si(R³)₃, N(R³)₂, or OR³ group of up to20 carbon or silicon atoms, and optionally two adjacent R² groups can bejoined together, thereby forming a fused ring structure, especially anindenyl ligand or a substituted indenyl ligand; R³ is independentlyhydrogen, a hydrocarbyl group, a trihydrocarbylsilyl group or atrihydrocarbylsilylhydrocarbyl group, said R³ having up to 20 atoms notcounting hydrogen; and Y is nitrogen or phosphorous.
 3. A metal complexaccording to claim 2, formula 4, wherein M is in the +4 oxidation state,j=2 and Q independently each occurrence is halide, hydride, hydrocarbyl,silylhydrocarbyl, hydrocarbyloxide, or dihydrocarbylamide, said Q havingup to 20 atoms not counting hydrogen, or two Q groups together form analkanediyl group or a conjugated C₄₋₄₀ diene ligand that together with Mform a metallocyclopentene.
 4. A metal complex according to claim 2,formula 5 wherein M is in the +3 oxidation state, j=1 and Q is either 1)a monovalent anionic stabilizing ligand selected from the groupconsisting of alkyl, cycloalkyl, aryl, silyl, amido, phosphido, alkoxy,aryloxy, sulfido groups, and mixtures thereof, said Q being furthersubstituted with an amine, phosphine, ether, or thioether containingsubstituent able to form a coordinate-covalent bond or chelating bondwith M said ligand having up to 50 atoms not counting hydrogen; or 2) aC₃₋₁₀ hydrocarbyl group comprising an ethylenic unsaturation able toform an η³-bond with M.
 5. A metal complex according to claim 2, formula6 wherein M is in the +3 oxidation state, in formula 6, j=2, Qindependently each occurrence is halide, hydride, hydrocarbyl,silylhydrocarbyl, hydrocarbyloxide, dihydrocarbylamide, said Q having upto 20 atoms not counting hydrogen, or two Q groups are joined togetherto form an alkanediyl group or a conjugated C₄₋₄₀ diene ligand which iscoordinated to M in a metallocyclopentene fashion.
 6. A metal complexaccording to claim 2, formula 4 wherein M is in the +2 oxidation state,j=1 and Q is a neutral conjugated diene, optionally substituted with oneor more tri(hydrocarbyl)silyl or tri(hydrocarbylsilyl)hydrocarbylgroups, said Q having up to 40 carbon atoms and forming a π-complex withM.
 7. A metal complex according to claim 3 wherein M is zirconium, Z isindium, and Q is chloride, methyl or trimethylsilylmethyl.
 8. A metalcomplex according to claim 6 wherein M is zirconium, Z is indium, and Qis 1,4-diphenyl-1,3-butadiene.
 9. A metal complex according to claim 8which is1,3-diisopropyl-2-t-butyl-amidinato[bis-(2-methyl-4-phenyl-indene)]indium] zirconium (1,4-diphenyl-1,3-butadiene).
 10. An olefinpolymerization process comprising contacting one or more olefin monomersunder polymerization conditions with a catalyst composition comprising ametal complex according to any one of claims 1-9.
 11. The process ofclaim 10 wherein the catalyst composition additionally comprises anactivating cocatalyst.
 12. The process of claim 11 conducted undersolution, slurry or high pressure polymerization conditions.
 13. Theprocess of claim 12 conducted under slurry or gas phase polymerizationconditions, wherein the catalyst additionally comprises an inert,particulated support.